Spectral Investigations on Cu<Superscript>2+</Superscript>-Doped ZnO Nanopowders

Cu²⁺-doped ZnO nanopowders, synthesized at room temperature by mild and simple solution method, are characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), optical, electron paramagnetic resonance (EPR) and Fourier-transform infrared (FT-IR) techniques. From XRD and SEM, the crystal structure is identified as hexagonal, and the average crystallite size is around 53 nm. Lattice cell parameters are evaluated. The optical and EPR spectral investigations suggest that the Cu²⁺ ion enters the host lattice in two tetragonally distorted octahedral sites. Crystal field, tetragonal field, spin Hamiltonian and bonding parameters are estimated.     

A Dual-Target Fluorescent Probe with Response-Time Dependent Selectivity for Cd<Superscript>2+</Superscript> and Cu<Superscript>2+</Superscript>

A novel fluorescent probe (NT) was developed by merging 2-hydrazinylbenzothiazole with 2-hydroxy-1-naphthaldehyde for the detection of Cd²⁺ and Cu²⁺. The probe alone is almost nonfluorescent due to the isomerization of C=N in the excited state. The addition of Cd²⁺ can cause an immediate strong green fluorescence owing to the suppression of C=N isomerization by Cd²⁺-coordination. Furthermore, NT gives a delayed turn-on fluorescence response to Cu²⁺ although it is a vigorous fluorescence quencher, which was thanks to the inhibition of the electron transfer between excited fluorophore and paramagnetic Cu²⁺ by sulfur donor. Based on fluorescence spectra and ESI-MS analysis, the binding modes between NT and Cd²⁺/Cu²⁺ were proposed.     

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 Novel Chemosensor Based on Rhodamine Derivative for Colorimetric and Fluorometric Detection of Cu<Superscript>2+</Superscript> in Aqueous Solution

A new rhodamine-based reversible chemosensor (2) was synthesized, which exhibits high sensitivity and selectivity for Cu²⁺ but no significant response toward other competitive metal ions in aqueous solution. Upon the addition of Cu²⁺, the spirolactam ring of 2 was opened and the solution color changed from colorless to red. Strangely, an unexpected fluorescence quenching was observed, which is contrary to the fluorescence turn-on of the most rhodamine-based chemosensors. The likely novel sensing mechanism has been proposed.     

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⁺.     

Recognition of H<Subscript>2</Subscript>PO<Stack><Subscript>4</Subscript><Superscript>-</Superscript></Stack> and Cu<Superscript>2+</Superscript> in Water by Luminescent Terbium Silica Xerogel

Terbium silica hybrid material with imidazole ring that can be emissive in water has been designed and showed host-guest interactions with specific ions (cations and anions). In detail, we studied the sensing abilities of this material by addition of the anions H₂PO₄^-, HSO₄^-, F^-, Cl^-, Br^- and I^- to water suspension of the derived powders. Only dihydrogen phosphate resulted in the quenching of the lanthanide luminescence (detection limit 10^-5 M). The same way was found in Cu²⁺ ions which also gave rise to luminescence quenching (detection limit 10^-5 M). More interestingly, luminescent sol-gel films were successfully prepared by the same materials and exhibited emission responses to H₂PO₄^- and Cu²⁺. For the sake of improving its mechanical property, the robust and flexible inorganic/PMMA hybrid material with sensing capability was also developed for future use.     

A highly Selective Fluorescent Sensor for Monitoring Cu<Superscript>2+</Superscript> Ion: Synthesis,Characterization and Photophysical Properties

A new fluorescent sensor, 4-allylamine-N-(N-salicylidene)-1,8-naphthalimide (1), anchoring a naphthalimide moiety as fluorophore and a Schiff base group as receptor, was synthesized and characterized. The photophysical properties of sensor 1 were conducted in organic solvents of different polarities. Our study revealed that, depending on the solvent polarity, the fluorescence quantum yields varied from 0.59 to 0.89. The fluorescent activity of the sensor was monitored and the sensor was consequently applied for the detection of Cu²⁺ with high selectivity over various metal ions by fluorescence quenching in Tris-HCl (pH = 7.2) buffer/DMF (1:1, v/v) solution. From the binding stoichiometry, it was indicated that a 1:1 complex was formed between Cu²⁺ and the sensor 1. The fluorescence intensity was linear with Cu²⁺ in the concentration range 0.5–5 μM. Moreso, the detection limit was calculated to be 0.32 μM, which is sufficiently low for good sensitivity of Cu²⁺ ion. The binding mode was due to the intramolecular charge transfer (ICT) and the coordination of Cu²⁺ with C = N and hydroxyl oxygen groups of the sensor 1. The sensor proved effective for Cu²⁺ monitoring in real water samples with recovery rates of 95–112.6 % obtained.     

Analysis of <Superscript>4</Superscript>He+<Superscript>40</Superscript>Ca and <Superscript>4</Superscript>He+<Superscript>44</Superscript>Ti scattering using different optical model potentials

Elastic scattering of ⁴He+⁴⁰Ca and ⁴He+⁴⁴Ti reactions at backward angles has been analyzed using two differentmodels, microscopic and semimicroscopic folding potentials. The derived real potentials supplemented with phenomenological Woods–Saxon imaginary potentials, provide good agreement with the experimental data at energy E_c.m. = 21.8 MeV without need to renormalize the potentials. Coupledchannels calculations are used to extract the inelastic scattering cross section to the low-lying state 2+ (1.083 MeV) of ⁴⁴Ti. The deformation length is obtained and compared with the electromagnetic measurement values as well as those obtained from previous studies.     

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.     

Physical and Spectral Investigations of Cu<Superscript>2+</Superscript>-Doped Alkali Zinc Borate Glasses

Physical and spectral studies on 20ZnO + xLi₂O + (30-x)Na₂O + 50B₂O₃ (5 ≤ x ≥ 25) doped with 0.1 mol% of paramagnetic CuO impurity are carried out. Powder X-ray diffraction patterns of the glass samples confirm the amorphous nature. The physical parameters of all the glasses were also evaluated with respect to the composition. The electron paramagnetic resonance spectra of all these glasses exhibit resonance signals that are characteristic of Cu²⁺ ions. The optical absorption spectra also confirm the Cu²⁺ ion in tetragonally elongated octahedral site. Various crystal field, spin-Hamiltonian and bonding parameters are evaluated. It is observed that the mixed alkali effect is significant.     

An EPR Study of Cu<Superscript>2+</Superscript> Doped Portlandite,Brucite and Hydrotalcite

The powder EPR spectra of portlandite (Ca(OH)₂), brucite (Mg(OH)₂) and hydrotalcite ([Mg₃Al(OH)₈]⁺[0.5CO ₃ ^- ·nH₂O]^-), doped with ⁶³CU²⁺, have been measured as a function of temperature. In all materials a static, temperature independent Jahn-Teller site and a dynamic, temperature dependent Jahn-Teller site was observed. In the rapidly reorienting situation the EPR spectrum of the dynamic site is still anisotropic. From the observed anisotropy it could be inferred that the hydroxyde ions surrounding the Cu²⁺ ion are situated at the vertices of an elongated octahedron which is compressed along its trigonal axis (c-axis). The angle between the axis of elongation of the Cu octahedra and the c-axis turned out to be 490 both for portlandite and brucite. The temperature range over which the averaged dynamic site could be observed varied considerably for the three materials.     

Self-assembled fractal hybrid dendrites from water-soluble anionic (thia)calix[4] arenes and Ag<Superscript>+</Superscript>

Novel water-soluble anionic p-tert-butylthiacalix[4]arene with propanesulfonate fragments has been synthesized. Alkylation of the lower rim of thiacalix[4]arene in the presence of NaH/THF led to cone conformation instead of the expected 1,3-alternate conformer due to metal template effect. The presence of supramolecular associates at the critical micelle concentration of 1.65 · 10^?5 M were investigated in aqueous solutions by a combination of different techniques (DLS and conductivity). It was observed that the macrocyclic platform decreases the CMC by tenfold as compared with non-macrocycle analogs. A simple approach for the design of stable monodisperse Ag-based nanoaggregates (near 95 nm) containing ionic Ag and organic ligand–thiacalix[4]arene sulfo derivative in water has been developed. Self-assembled fractal hybrid nanodendrites consisting of water-soluble anionic (thia)calix[4]arenes and Ag⁺ have been obtained in a single step under mild conditions.

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Preparation of Cu<Superscript>2+</Superscript>/NTA-derivatized branch polyglycerol magnetic nanoparticles for protein adsorption

In this report, we described the preparation of Cu²⁺/nitrilotriacetic acids (NTA)-derivatized branch polyglycerol magnetic nanoparticles for protein adsorption with avoidance of nonspecific interactions at the same time. Magnetic nanoparticles (MNPs) were synthesized by the coprecipitation method. The transmission electron microscopy results showed that the average diameter of MNPs was 15.8 ± 4.6 nm. X-ray photoelectron spectroscopy and Fourier Transform infrared measurements indicated that branch polyglycerols were grafted on MNPs via the ring-opening polymerization of glycidol and that Cu²⁺ ions had been successfully immobilized on the surface of MNPs. The protein immobilization effect was characterized by UV–Vis spectrum. The results proved that Cu²⁺/NTA-derivatized branch polyglycerol magnetic nanoparticles effectively adsorbed bovine haemoglobin and rarely adsorbed lysozyme and γ-globin.     

Synthesis and Properties of a Novel FRET-Based Ratiometric Fluorescent Sensor for Cu<Superscript>2+</Superscript>

A novel FRET-based probe LS3 was designed and synthesized. As expected, it exhibited high selectivity and sensitivity for detecting Cu²⁺ over other commonly coexistent metal ions. The detection limit was measured to be 0.0423 μM for Cu²⁺, which can meet the selective requirements for practical application. In addition, the newly synthesized compound 3a/b have potential value of further synthesizing more analogous FRET-based probes.     

Paramagnetic resonance and off-center location of Cu<Superscript>2+</Superscript> ions in ferroelectric lead germanate

This paper reports on the results of investigations into the orientation behavior of the splitting of the electron paramagnetic resonance spectrum due to the location of paramagnetic ions in different domains of Cu²⁺-containing lead germanate. The off-diagonal components of the tensor g for Cu²⁺ quasi-monoclinic centers are determined. A model for off-central displacement of copper ions is proposed with due regard for the revealed symmetry of paramagnetic centers, their superhyperfine structure, and the orientation of the magnetic axes.     

Electron paramagnetic resonance of Ce<Superscript>3+</Superscript> and Nd<Superscript>3+</Superscript> impurity ions in YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>6.13</Subscript>

The electron paramagnetic resonance (EPR) spectra of Ce³⁺ and Nd³⁺ impurity ions in unoriented powders of the YBa₂Cu₃O_6.13 compound are observed and interpreted for the first time. It is demonstrated that, upon long-term storage of the samples at room temperature, the EPR signals of these ions are masked by the spectral line (with the g factor of approximately 2) associated with the intrinsic magnetic centers due to the significant increase in its intensity.     

Synthesis and Evaluation of a Schiff-Based Fluorescent Chemosensors for the Selective and Sensitive Detection of Cu<Superscript>2+</Superscript> in Aqueous Media with Fluorescence Off-On Responses

Copper being an essential nutrient; also pose a risk for human health in excessive amount. A simple and convenient method for the detection of trace amount of copper was employed using an optical probe R1 based on Schiff base. The probe was synthesized by Schiff base condensation of benzyl amine and 2-hydroxy-1-napthaldehyde and characterized by single X-ray diffraction, ¹H NMR and FTIR. By screening its fluorescence response in a mixture of DMSO and H₂O (20:80, v/v) R1 displayed a pronounced enhancement in fluorescence only upon treatment with copper. Other examined metal ions such as alkali, alkaline and transition had no influence. Within a wide pH range 5–12 R1 could selectively detect copper by interrupting ICT mechanism that results in CHEF. From Job’s plot analysis a 2:1 binding stoichiometry was revealed. The fluorescence response was linear in the range 1–10?×?10^?9 M with detection limit 30?×?10^?9 M. Association constant was determined as 1?×?10¹¹ M^?2 by Benesi-Hilderbrand plot. As a fast responsive probe it possesses good reproducibility and was employed for detection of copper in different water samples.     

Blocking of coupling to the 0<Subscript>2</Subscript><Superscript>+</Superscript> excitation in <Superscript>154</Superscript>Gd by the [505]11/2<Superscript>-</Superscript> neutron in <Superscript>155</Superscript>Gd

The concept that the first excited 0⁺ states in N = 90 nuclei are not a b \beta -vibration but a second vacuum formed by the combination of the quadrupole pairing force and the low density of oblate orbitals near the Fermi surface is supported by the blocking of this collective mode in ¹⁵⁴Gd from coupling to the [505]11/2^- single-particle quasi-neutron orbital in ¹⁵⁵Gd . The coupling of this orbital to the 2⁺ g \gamma -vibration in ¹⁵⁴Gd is observed since this coupling is not Pauli-blocked.     

luminescence of BaGa<Subscript>2</Subscript>Se<Subscript>4</Subscript> crystals activated by Eu<Superscript>2+</Superscript> and Ce<Superscript>3+</Superscript> ions

We have studied the effect of doping with Eu²⁺ and Ce³⁺ ions on the photoluminescence (PL) of BaGa₂Se₄ crystals in the temperature range 77–300 K. We have established that the broad bands with maxima at wavelengths 456 nm and 506 nm observed in the photoluminescence spectra of BaGa₂Se₄:Ce³⁺ crystals are due to intracenter transitions 5d → ²F_7/2 and 5d →²F_5/2 of the Ce³⁺ ions, while the broad photoluminescence band with maximum at 521 nm in the spectrum of BaGa₂Se₄:Eu²⁺ is associated with 4f⁶ 5d → 4f⁷ (⁸S_7/2) transitions of the Eu²⁺ ion. We show that in BaGa₂Se₄:Eu²⁺,Ce³⁺ crystals, excitation energy is transferred from the Ce³⁺ ions to the Eu²⁺ ions.