Synthesis and Characterization of CdS Nanoparticles with Strong Electrolyte Behavior

The CdS nanoparticles whose structure is similar to a strong electrolyte were synthesized by the colloidal chemical method. The CdS nanoparticles with Cd²⁺-rich surface are capped by the electrically neutral ligand of 2,2-bipyridine (bpy), and the counterion, BPh₄ ^-, is adsorbed around the particle as balance charge. The donation from 2,2-bipyridine at 2-position to the Cd²⁺-rich surface of the CdS nanoparticles was characterized by X-ray photoelectron spectroscopy (XPS). These CdS nanoparticles can redisperse in pyridine (py) or DMF, and have high stability. The determination of electroconductivity and the electrophoresis deposition in dilute solution containing the CdS nanoparticles further prove the rationality of the above electrolyte structure of the CdS nanoparticles.     

Hybrid system of iron porphyrin on aminosilanized c-Si

Adsorption of iron porphyrin (Fe^IIITPPS₄) Fe(III)meso-tetra(4-sulfonatophenyl) porphine on aminosilanized surface of crystalline Si (c-Si) was investigated. Formation of nanometric structures of Fe^IIITPPS₄ on c-Si, the surface of which has been modified by various silanization procedures, was studied. Aqueous, ethanol and acetone solutions of 3-aminopropyltrietoxysilane (APTES) were prepared for deposition on c-Si by spinning or immersion techniques. Smooth homogeneous APTES films of thickness 100–500 nm were produced by multiple spin coating procedure. Thin APTES films of thickness 2.5 nm were fabricated by dipping technique followed by washing procedure. Hybrid system of Fe^IIITPPS₄/APTES/Si was prepared from a drop of Fe^IIITPPS₄ aqueous solution put on aminosilanized Si surface or by dipping the Si wafer in Fe^IIITPPS₄ aqueous solution. Nanostructures of size 50–250 nm were formed along with large rings of Ø50–100 μm which have been observed at chemisorption of highly concentrated (1 mM) Fe^IIITPPS₄ aqueous solution. Spectroscopic ellipsometry was used to characterize the APTES layer and to investigate the aggregation state of Fe^IIITPPS₄. The studies provided allowed one to presume that covalent bonds were formed between amino-groups of APTES and functional groups of sulfonic acid in porphyrin leading to immobilization of Fe^IIITPPS₄ on Si substrate.     

Calibration methods and avoidance of errors in measurement of intracellular pH (pHcyt) using the indicator bis(carboxyethyl)-5(6)-carboxyfluorescein (BCECF) in human platelets

Determinations of pH_cyt in suspensions of human platelets using BCECF [bis(carboxyethyl)-5(6)-carboxyfluorescein] can be seriously biased by leakage of the fluorescent indicator. Two methods (pH jump and Mn²⁺) are presented for determining the fraction of external indicator (B _ext) and eliminating this error. Both methods rely on rapid perturbations (pH jump or Mn²⁺ addition), which affect the fluorescence of the external dye immediately and the intracellular dye more slowly. Identical values ofB _ext are reported. Failure to correct for dye leakage can result in overestimation of pH_cyt by as much as 0.4 unit at physiological external pH (pH_ext). Two methods of calibration of the cytoplasmic signal were compared after correcting forB _ext: the digitonin lysis method and the nigericin calibration method. In the digitonin method the dye is released at the end of the experiment and the dependence of its fluorescence is determined as a function of pH. The method assumes that the fluorescence and titration characteristics of the dye in the cytoplasm are not different from those in solution. It gives pH_cyt=6.75±0.07 for pH_ext=7.3. In the nigericin method, 150 mM external K⁺ and 10 M nigericin are used for the purpose of setting pH_cyt=pH_ext to accomplish anin situ calibration. The method was complicated by extra leakage induced by nigericin. Assuming that the ionophore could equilibrate pH in the alkaline range, the fluorescence of the anionic form of BCECF in the cytoplasm would be 15% lower than in solution and pH_cyt would be 0.3 unit higher than presented above. A number of observations favor the digitonin lysis method of calibration. The fluorescence polarization of BCECF in platelets is small and indistinguishable from that in solution (0.000±0.022). The spectrofluorimetric characteristics of the intracellular dye are identical to those in solution (150 mM NaCl or KCl). There was no evidence for self-quenching or binding to cellular elements for cytoplasmic BCECF concentrations up to 1.8 mM. The following agents are capable of introducing error: (1) the Na⁺ substituteN-methyl-d-glucamine doubles theK _d and decreases by 13% the F _max of BCECF; (2) the Na⁺/H⁺ exchange inhibitor amiloride quenches BCECF fluorescence and is intrinsically fluorescent; and (3) bovine serum albumin (used to remove nigericin) quenches external BCECF with kinetics mimicking acidification of the cytoplasm.     

Large third-order nonlinear optical properties of C70 fullerene in the infrared regime

The nonlinear third-order optical susceptibility of C₇₀ in a toluene solution is measured for the first time by the method of degenerate four-wave mixing using 10 ns laser pulses at 1.06 m. The third-order susceptibility X _in ⁽³⁾ is 5.6×10^–12 esu for a C₇₀ toluene solution at a concentration of 0.476 g/l. The correspondent magnitude of the hyperpolarizability ₁₁₁₁ of the C₇₀ molecule is 1.2×10^–30 esu which is in a good agreement with the prediction given by the model of a free electron in a spherical box.     

A Novel Ratiometric Fluorescent Mercury Probe Based on Deprotonation-ICT Mechanism

A new NBD-rhodamine dye (1) was developed as a colorimetric and ratiometric fluorescent chemosensor for Hg²⁺ with good selectivity in aqueous ethanol solutions under neutral to basic conditions. Sensor 1 showed absorption at 468 nm and a weak emission at 529 nm (? _F ?=?0.063) in ethanol/aqueous tris buffer (9:1, v/v) of pH 9.17 solution. Bathochromic shifts in both absorption (492 nm) and fluorescence spectra (569 nm, ? _F ?=?0.129), respectively upon addition of 2 equiv. of Hg²⁺ were observed. The ring-opening reaction of the spirolactam form to the corresponding xanthene form was not found. The interaction of Hg²⁺ with chemosensor 1 resulted in the deprotonation of the secondary amine conjugated to the NBD component so that the electron-donating ability of the N atom was enhanced. Deprotonation-ICT mechanism of secondary amines was suggested for the ratiometric fluorescent chemosensing for 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.     

Flame-synthesized Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Tb<Superscript>3+</Superscript> nanocrystals as spectral converting materials

In flame spray pyrolysis (FSP), the generation of uniform nanoparticles can be quite challenging due to difficulties in controlling droplet sizes during liquid spraying and uneven flame temperature. Here, we report a method to produce relatively uniform nanocrystals of a Tb³⁺ doped Y₂O₃ phosphor. In ethanol, metal nitrate precursors were simply mixed with organic surfactants to form a homogeneous solution which was then subjected to FSP. Depending on relative concentrations of the surfactant (oleic acid) to the metal precursors (yttrium and terbium nitrates), different sizes and morphologies of Y₂O₃:Tb³⁺ particles were obtained. By adjusting the surfactant concentration, Y₂O₃:Tb³⁺ crystals as small as 20~25 nm were acquired. X-ray diffraction and transmittance electron microscopy were used to prove that as-synthesized nanoparticles were highly crystalline due to the high temperature of FSP. X-ray photoelectron spectroscopy revealed that terbium dopants were well distributed throughout Y₂O₃ particles and a small portion of carbonate impurities were remained on the surface of particles, presumably originated from incomplete combustion of the organic surfactants. Photoluminescence (PL) spectra of Y₂O₃:Tb³⁺ nanocrystals exhibited a green light emission ensuring that the terbium doping was successfully occurred. However, when post-annealing was performed on the nanocrystals, their PL was dramatically enhanced indicating that quenching centers such as carbonate impurities and surface defects may have been removed by the annealing process. Owing to the continuous processability of FSP, this current method can be a practical way to produce nanoparticles in a large quantity. The obtained Y₂O₃:Tb³⁺ nanocrystals were used to fabricate a transparent film with poly-ethylene-co-vinyl acetate (poly-EVA) polymer, which was suitable for a spectral converting layer for a solar cell.

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Spectral-Luminescent Studies of the “Photolon” Photosensitizer in Model Media and in Blood of Oncological Patients

Using the methods of steady-state absorption and fluorescence spectroscopy and flash-photolysis, the new photosensitizer Photolon (Stock Company Belmedpreparaty) and its basic chromophore part — the substance chlorin e ₆ — have been studied under model conditions. It has been shown that there are no considerable differences between the spectral-luminescent characteristics of Photolon and chlorin e ₆ at a concentration not exceeding 2.5·10^–5 M in ethanol, phosphate-saline buffer (pH 8.5), and isotonic solution. That is, the polyvinyl-pyrrolidone (PVP) entering into the composition of Photolon does not influence the chromophore characteristics being investigated. It has been found that an increase in the mass fraction of PVP in the buffer solution of chlorin e ₆ leads to an increase in the degree of polarization of chlorin e ₆ fluorescence and to a change in the spectral-luminescent and kinetic characteristics, pointing to the fact that the pigment is built into the hydrophobic portions of the polymer. Using the method of multiple scattering of light, it has been shown that both Photolon and chlorin e ₆ are present in the whole blood of donors and oncological patients mainly in the monomeric form; Photolon is quickly removed from the blood of patients (after 24 h, C 10^–3 mg/ml).     

Synthesis of nano-sized polycrystalline PZT powders using molecular building blocks by designed chemical route

Polycrystalline perovskite Pb(Zr _x Ti O₃ (PZT) powders in the form of particles with sizes in the range 2∼ ∼10 nm were obtained by hydrolysis of a mixed metal alkoxide precursor. The mixed metal alkoxide precursor was synthesized by refluxing Pb(OAc)₂, Zr(O– ⁿ Bu)₄ and Ti(O–ⁱPr)₄ in anhydrous ethanol. After it was hydrolyzed in a solution with a pH of 3 and dried at 423 K, nano-sized polycrystalline perovskite PZT was obtained. This temperature of formation of the PZT perovskite phase is noticeably lower than those reported elsewhere. The sizes of the freshly dried polycrystalline perovskite PZT particles are within the range of 2–5 nm.     

Molecular mobility of nanocellulose hydrogels

The molecular mobility of nanocellulose hydrogels isolated from microcrystalline cellulose is evaluated using the spin probe method, from the correlation time τ (s) and rotational frequency ν = 1/τ(s^–1) of stable nitroxyl radicals introduced into the medium under study. In an aqueous gel medium, the EPR spectrum of the probe features an anisotropic triplet of frozen particles over a temperature range of 77 to 265 K. In an aqueous–ethanolic gel solution, the temperature of onset of rotation of the radical is 85 K lower. The rotational correlation time is determined from the parameters of the EPR spectrum recorded in the temperature range of 180–290 K. The resulting Arrhenius temperature dependence logν = f(1/T) is used to evaluate the activation energy of rotation E of the radical and the preexponential factor ν₀(s^–1), the frequency of rotational vibrations of the particle around the equilibrium position. For the aqueous medium, E = 11.2 kcal/mol; in the presence of ethanol, E = 5.2 kcal/mol; the preexponential factors for the aqueous and aqueous–ethanolic media are ν₀ = 7 × 10¹⁸ and 6 × 10¹⁴ s^–1, respectively. The parameters E and ν₀ measured in the pure solvents and in the samples containing nanocellulose differ little, which is indicative of a high hydrophobicity of the probe molecule (and hydrogel particles) and of their weak interaction with the environment. The high value (~10¹⁸ s^–1) of the preexponential factor is explained in terms of the compensation effect of water.     

Processes of Electron Excitation Energy Conversion in Europium Tris‐Naphthoyltrifluoroacetonate

The absolute quantum yield and duration of ⁵ D ⁷ F _j luminescence of the Eu³⁺ ion in europium trisnaphthoyltrifluoroacetonate has been measured on excitation of luminescence in the UV S ₀ S ₁ absorption band of the ligand in the temperature range 77–365 K. Based on the analysis of the experimental dependences obtained and solution of the balance equations for stationary and nonstationary cases, we have developed a new approach to the determination of the scheme and rate constants of actual transitions. The rate constants of all processes of electron excitation energy conversion have been determined. The role of the state with charge transfer in these processes has been revealed.     

Semiempirical QSAR study and ligand receptor interaction of estrogens

Softness values E_n of estrogen derivatives and softness values E_m of receptor lysine, histidine, tyrosine and cysteine have been evaluated by Klopman equation. The required parameters for the solution of Klopman equation have been calculated with the help of PM3 method. The difference E_nm between E_n and E_m has been derived for QSAR study. The estrogen derivatives have been divided into four different sets on the basis of their structural similarities, and their biological activity taken from literature in terms of relative binding affinity (RBA). The QSAR study shows that, E_nm values provide good relationship with biological activity.     

Fluorimetric Determination of Thyroxine Hormone with Eu(III)-(Pyridine-2,6-Dicarboxylate) Tris Complex

We describe a method for the determination of thyroxine (Thy) using its quenching effect on Eu(PDA)₃ ^3- tris complex fluorescence. The relative fluorescence intensities are measured at fixed _exc = 282 nm, _em = 615 nm by titrating the metal complex with Thy in piperazine buffer solution at pH 6.5. Data indicated an associative type of reaction of two molecules valid between 0.0 < R < 1.0, R being the mole ratio of Eu(PDA)₃ ^3- to Thy. Over this ratio and up to (R 1.0) collisional quenching of Eu(PDA)₃ ^3- complex ion emission is seen as a result of heavy atom effect, intermolecular energy transfer playing the main role. This is also confirmed by the Stern-Volmer equation. In optimized experimental conditions, the L- form of Thy is determined in a range of 15.5–551.6 g/ml (2.0 × 10^–5 – 7.1 × 10^–4 M) with relative error of ±1.17%.     

Effect of phase transition and particle size on thermoluminescence characteristics of nanocrystalline K2Ca2(SO4)3:Cu+ phosphor

A new K₂Ca₂(SO₄)₃:Cu⁺ nanocrystalline TLD phosphor was prepared by chemical coprecipitation method using calcium chloride, potassium chloride and ammonium sulphate as reactants and copper chloride (Cu₂Cl₂, as impurity) in the presence of ethanol. The samples were characterized by X-ray diffraction (XRD), Transmission electron microscopy (TEM), Differential thermal and thermogravimetric analysis (DT-TGA) techniques. XRD and DTA data show that there is a phase transformation from orthorhombic to cubic occurring at around 550 K. The effects of impurity concentration, annealing temperature and γ rays dose on TL characteristics of the material have been studied. Different glow curves have been theoretically deconvoluted using computerized glow curve deconvolution (CGCD method) into simple glow peaks to determine their trapping parameters. The results show that different phases existing in the material on annealing might have reorganized the electron-traps (energy levels) and hole-traps (luminescence centers) and are responsible for changing glow curve structures. This is very important to know as any change in the glow curve structure would cause errors in estimation of doses of high-energy radiations and also may lose its reusability. The photoluminescence (PL) studies show that there are no redox reactions (Cu⁺

Cu²⁺) taking place and Cu remains in its Cu⁺ form after annealing and even after irradiation.     

Nonlinear refraction and nonlinear absorption of As2S3 aqueous solution

We report for the first time to our knowledge on the preparation of colloidal solution of chalcogenide semiconductor As₂S₃ by laser ablation and the measurements of its nonlinear-optical characteristics using Z-scan method at the wavelength of Nd:YAG laser radiation ( = 1064 nm, = 25 ns). The nonlinear refractive index was measured to be –7.5 × 10^–18 m² W^–1. Nonlinear absorption coefficient of chalcogenide solution was measured to be 1 cm GW^–1.     

Electroless gold deposition on silicon(100) wafer based on a seed layer of silver

This article describes a method of electroless gold deposition on a Si(100) wafer having a silver surface as seed layer. The seed layer was firstly deposited onto the surface of an etched wafer in an acidic solution of 0.005 mol/L AgNO₃+0.06 mol/LHF. The electroless gold deposition is performed by immersing the Ag-activated wafer in an electroless bath with a composition of 1.27×10^-3 mol/L[AuCl₄]^-+2.00×10^-2 mol/LNaH₂PO₂+8.32×10^-2 mol/L NH₂CH₂CH₂NH₂ (pH = 9.0–9.5). The bath temperature is 50–70 °C. The morphology of the seed layer and the gold film were characterized by atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS).PACS 82.45.Mp; 81.15.Pq; 81.10.Dn     

The quadratic Lagrangians in General Relativity

The solutions of the General Relativity equations with quadratic LagrangiansR _iklmR^iklm, R_ikR^ik, R² are studied. It is shown that nontrivial Euclidian (atr ) solution of the theory equations does not exist whenT0 (T is a trace of the energy-momentum tensor of matter). The Schwarzschild solution is not an external part of a total solution whenT0. Under conditionT=R=0 LagrangiansR _iklmR^iklm, R_ikR^ik lead to the identical field equations, so there exist the only quadratic Lagrangian and the only field equations. This equation has a solution with an external part being a standard Schwarzschild solution for the statical spherically symmetric case.     

EPR study of impurity iron ion clusters in BaF<Subscript>2</Subscript> crystals

Tetragonal paramagnetic centers with spin S = 7/2 were detected in x-ray-irradiated BaF₂: Fe (c_Fe ≈ 0.002 at. %) crystals using the EPR method. Electronic transitions between the |±1/2〉 states of a Kramers doublet were observed in the X and Q ranges. In the EPR spectra of the tetragonal centers, a ligand hyperfine structure (LHFS) was observed corresponding to the interaction of the electron magnetic moment of the tetragonal center with eight equivalent ligands. The large spin moment, significant anisotropy of the magnetic properties, and the characteristic LHFS indicate that the tetragonal center is a Fe^1.5+?Fe^1.5+ dimer in which the two iron ions are bound via superexchange interaction. It is assumed that, before crystal irradiation, this dimer was in the Fe³⁺(3d⁵)?Fe⁺(3d⁷) state.     

Sum frequency beam analysis for the determination of the temporal characteristics of ultrashort light pulses

An extension of the single-shot second harmonic beam method proposed earlier for picosecond pulse duration measurements is presented for the case of two incident pulses of differing frequencies, durations and transverse sizes. The solution of the wave equation for noncollinear sum frequency generation in a nonlinear crystal by two Gaussian, spatially limited ultrashort pulses is given. It is shown that the width ( ₁ ² + ₂ ² )^1/2 of the temporal cross-correlation function of the two pulses can be deduced from the spatial energy distribution of the sum frequency beam. The method can be used e.g. in the case of a relatively weak secondary pulse obtained in some nonlinear processes. Preliminary experimental results demonstrating the possibilities offered by the method are presented.