Fluorescence “turn-on” chemosensor for the selective detection of zinc ion based on Schiff-base derivative

N,N′-phenylenebis(salicylideaminato) (L) has been used to detect trace amounts of zinc ion in acetonitrile–water solution by fluorescence spectroscopy. The fluorescent probe undergoes fluorescent emission intensity enhancement upon binding to zinc ions in MeCN/H₂O (1:1, v/v) solution. The fluorescence enhancement of L is attributed to the 1:1 complex formation between L and Zn(II), which has been utilized as the basis for selective detection of Zn(II). The linear response range for Zn(II) covers a concentration range of 1.6 × 10^?7 to 1.0 × 10^?5 mol/L, and the detection limit is 1.5 × 10^?7 mol/L. The fluorescent probe exhibits high selectivity over other common metal ions, and the proposed fluorescent sensor was applied to determine zinc in water samples and waste water.     

Fluoride affinities of fluorinated alanes

The fluoride affinities of fluorinated alanes, AlH_mF_3?m (m = 1–3) were measured using energy-resolved collision-induced dissociation of fluorinated aluminate anions. The AlH_mF_4?m^? anions were formed by reaction of dimethylethylamine-alane with fluoride ion and F₂. From the measured bond dissociation energies, the fluoride affinities of fluorinated alanes are determined to be 93.2 ± 3.1, 97.5 ± 4.0, and 108.6 ± 3.7 kcal/mol for m = 3, 2, and 1, respectively. The fluoride affinities are in good agreement with the theoretical calculations at the CCSD(T)/CBS and B3LYP/6-31 + G* levels of theory. The increased Lewis acidity of more fluorinated alanes is attributed to increased positive charge density on the aluminum.     

Anion receptors with viologen molecular scaffold

We have designed and synthesized new anion receptors 1²⁺ and 2²⁺. These receptors interact with anions through hydrogen bonds and charge transfer complex depending on the basicity of anion. Therefore, anions with weak basicity such as chloride, bromide, and hydrogen sulfate bound to the receptors 1²⁺ and 2²⁺ only through hydrogen bonds while anions with strong basicity such as fluoride, acetate and dihydrogen phosphate bound to the receptors 1²⁺ and 2²⁺ only through charge transfer interactions at UV–vis titration condition (20 μM). However, in more concentrated ¹H NMR titration condition (2 mM), 1²⁺ and 2²⁺ decomposed to form the product one of their amide arm is eliminated. As charge transfer complexes showed colorimetric response, they turned out to be efficient naked eye detector for anions with strong basicity such as fluoride, acetate, and dihydrogen phosphate.     

Anthracene-based macrocyclic fluorescent chemosensor for selective sensing of dicarboxylate

An anthracene-based macrocyclic receptor has been designed and synthesized for selective recognition of 1,4-phenylenediacetate (K_a = 3.34 × 10⁵ M^?1). The macrocycle binds 1,4-phenylenediacetate selectively at the charged sites of the receptor with a concomitant increase in fluorescence of anthracene. The interaction properties of the macrocycle were evaluated by ¹H NMR, UV–vis and fluorescence spectroscopic methods.     

Fluorescence and DNA-binding spectral studies of neodymium(III) complex containing 2,2′-bipyridine, [Nd(bpy)2Cl3·OH2]

The interaction of [Nd(bpy)₂Cl₃·OH₂], where bipy is 2,2′-bipyridine, with DNA has been studied by absorption, emission, and viscosity measurements. [Nd(bpy)₂Cl₃·OH₂] showed absorption decreasing in charge transfer band with increasing of DNA. The binding constant, K_b has been determined by absorption measurement and found to be (1.5 ± 0.1) × 10⁵ M^?1. The fluorescent of [Nd(bpy)₂Cl₃·OH₂] has been investigated in detail. The interaction was also studied by fluorescence quenching technique. The results of fluorescence titration revealed that DNA had the strong ability to quenching the intrinsic fluorescence of Nd(III) complex at 327 nm. The binding site number n, apparent binding constant K_b and the Stern–Volmer quenching constant K_SV have been determined. Thermodynamic parameters have been calculated according to relevant fluorescent data and Van’t Hoff equation. Characterization of bonding mode has been studied. The results suggested that the major interaction mode between [Nd(bpy)₂Cl₃·OH₂] and DNA was groove binding.     

X-ray diffraction,spectroscopic (IR,Raman) and DSC studies of bis(betainium) p-toluenesulfonate monohydrate crystal

Bis(betainium) p-toluenesulfonate monohydrate (abbreviated as BBTSH) was studied at various temperatures by X-ray diffraction, differential scanning calorimetry and vibrational spectroscopy methods. DSC curves of BBTSH show a peak at about 349 K which corresponds to water escape from the crystal, and reveal the “cold crystallization” phenomenon. BBTSH crystallizes in the P2₁/c space group of monoclinic system. After heating above 349 K the compound dehydrates, the crystal system changes to triclinic, the monocrystalline samples become non-merohedral twins. The BBTSH crystal comprises p-toluenesulfonic anions, monoprotonated betaine dimers and water molecules. Three kinds of hydrogen bonds are present in the crystal: strong, asymmetric and almost linear OH⋯O hydrogen bond (R(O⋯O) = 2.463(2) Å), weak O_wH⋯O hydrogen bonds (R(O_w⋯O) = 2.820(2) − 2.822(2) Å) and weak CH⋯O hydrogen bonds (R(C⋯O) = 3.295(2) − 3.416(2) Å). The ν_aOHO vibration of the strongest hydrogen bond in the crystal gives rise to an intense broad absorption with numbers of transmission windows in the low wavenumber region of the infrared spectra. Coupling between νCO stretching vibrations of two COO groups of the betaine dimer was detected. The process corresponding to the loss of water is accompanied by the breakage of strong OH⋯O hydrogen bonds in betaine dimers and rearrangement inside half of the betaine dimers. This rearrangement results in formation of the new betaine dimers with OH∙∙∙O hydrogen bond of similar strength as corresponding bond in the hydrated form (BBTSH).     

Synthesis,characterization and batch assessment of groundwater fluoride removal capacity of trimetal Mg/Ce/Mn oxide-modified diatomaceous earth

In this study, trimetal Mg/Ce/Mn oxide-modified diatomaceous earth (DE) was synthesized at optimal conditions. Comparison of the SEM images and the results of EDX analyses of the raw and the modified DE confirmed the surface modification of the raw DE with the trimetal oxide. Groundwater fluoride removal capacity of the sorbent was evaluated by batch method at various defluoridation conditions. At a sorbent dosage of 0.6 g/100 mL (contact time: 60 min, mixing speed of 200 rpm and temperature: 297 K), the fluoride removal was >93% for solutions containing initial fluoride concentration of 10–60 mg/L. Sorbent’s optimum fluoride uptake capacity was 12.63 mg/g at the initial fluoride concentration of 100 mg/L. Fluoride removal was >91% for solutions with initial pH range of ∼4–11 (initial fluoride concentration: 9 mg/L, sorbent dosage: 0.6 g/100 mL). Appraisal of the effect of co-existing anions on fluoride removal showed that CO₃²⁻ would reduce the amount of fluoride removed from solution, while other anions such as PO₄³⁻, NO₃⁻ and SO₄²⁻ had no observable effect. K₂SO₄ solution was found to be most suitable for regeneration of spent Mg/Ce/Mn oxide-modified DE compared to Na₂CO₃ and NaOH. The mechanism of fluoride removal at pH > 5.45 (pHpzc = 5.45) occurred by exchange of hydroxyl groups on surface of sorbent with fluoride ions from solution. Sorption data fitted better to Langmuir isotherm and pseudo-second-order model. External diffusion was observed to be the sorption rate limiting factor.     

Experimental observations on the competing effect of tetrahydrofuran and an electrolyte and the strength of hydrate inhibition among metal halides in mixed CO2 hydrate equilibria

In the present work, experimental data on the equilibrium conditions of mixed CO₂ and THF hydrates in aqueous electrolyte solutions are reported. Seven different electrolytes (metal halides) were used in this work namely sodium chloride (NaCl), calcium chloride (CaCl₂), magnesium chloride (MgCl₂), potassium bromide (KBr), sodium fluoride (NaF), potassium chloride (KCl), and sodium bromide (NaBr). All equilibrium data were measured by using Cailletet apparatus. Throughout this work, the overall concentration of CO₂ and THF were kept constant at (0.04 and 0.05) mol fraction, respectively, while the concentration of electrolytes were varied. The experimental temperature ranged from (275 to 305) K and pressure up 7.10 MPa had been applied. From the experimental results, it is concluded that THF, which is soluble in water is able to suppress the salt inhibiting effect in the range studied. In all quaternary systems studied, a four-phase hydrate equilibrium line was observed where hydrate (H), liquid water (L_W), liquid organic (L_V), and vapour (V) exist simultaneously at specific pressure and temperature. The formation of this four-phase equilibrium line is mainly due to a liquid–liquid phase split of (water + THF) mixture when pressurized with CO₂ and the split is enhanced by the salting-out effect of the electrolytes in the quaternary system. The strength of hydrate inhibition effect among the electrolytes was compared. The results shows the hydrate inhibiting effect of the metal halides is increasing in the order NaF < KBr < NaCl < NaBr < CaCl₂ < MgCl₂. Among the cations studied, the strength of hydrate inhibition increases in the following order: K⁺ < Na⁺ < Ca²⁺ < Mg²⁺. Meanwhile, the strength of hydrate inhibition among the halogen anion studied decreases in the following order: Br^? > Cl^? > F^?. Based on the results, it is suggested that the probability of formation and the strength of ionic–hydrogen bond between an ion and water molecule and the effects of this bond on the ambient water network are the major factors that contribute to hydrate inhibition by electrolytes.     

Fused bis[2-(2′-hydroxyphenyl)benzoxazole] derivatives for improved fluoride sensing: The impact of regiochemistry and competitive hydrogen bonding

Development of fluorescent chemical sensors for fluoride is important due to increased use of fluoride in environment. A fused bis[2-(2′-hydroxyphenyl)benzoxazole] 5, which is capable of giving ESIPT emission, is found to be a useful fluorescent sensor for fluoride detection. Upon binding to fluoride, bis(HBO) 5 shows a large spectral shift in both fluorescence (from ～490 nm to ～440 nm) and absorption (from 353 nm to 392 nm). In comparison with the isomeric 4, bis(HBO) 5 dramatically improves the sensitivity in fluoride binding (by an order of magnitude), revealing a large impact of regiochemistry on the sensor performance. ¹H NMR has been used to study the fluoride binding, and to correlate the intramolecular hydrogen bonding with the fluoride response. Sensitivity of 5 towards fluoride is as low as 10^?5 M. Bis(HBO) 5 also showed excellent selectivity towards fluoride while being silent to other anions (Cl^?, Br^?, HS^? and PO₄^3?), thus making 5 a potentially useful probe.     

Electrochemical fabrication of novel fluorescent polymeric film: Poly(pyrrole–pyrene)

We describe herein the electrochemical characterization and polymerization of 4-pyren-1-yl-butyric acid 11-pyrrol-1-yl-decyl ester (pyrrole–pyrene) in CH₃CN. The electrochemical oxidation of the pyrrole group at 0.77 V vs Ag/Ag + 10 mM in CH₃CN led to the first example of a fluorescent polypyrrole film. The mechanism of deposition on platinum electrode was studied by voltammetry and chronoamperometry. The optical properties of the polymeric films electrogenerated on ITO electrodes were examined by UV–visible spectroscopy and fluorescence microscopy indicating an increase in fluorescence properties by increased polymer thickness. The electrochemical oxidation of pyrenyl group linked to the polypyrrole backbone was carried out at 1.2 V. This additional polymerization was demonstrated by UV–visible spectroscopy and induced the loss of the fluorescence properties of the resulting polymeric film.     

A highly selective fluorescent sensor for fluoride anion based on pyrazole derivative: Naked eye “no–yes” detection

A new pyrazole-based fluorescent sensor, 5-amino-3-(5-phenyl-1H-pyrrol-2-yl)-1H-pyrazole-4-carboxamide (compound 1), was studied for fluoride anion (F^?) detection in organic or water-containing solution. This compound displayed both changes in UV–vis absorption and fluorescence emission spectra upon addition of F^?. With increasing of F^?, blue emission intensity increases drastically and reaches saturation with 607-fold enhancement at 424 nm. The results indicate that compound 1 has highly selectivity for fluoride detection over other anions, such as Cl^?, Br^?, I^?, HSO₄^?, H₂PO₄^? and AcO^? in DMSO or aqueous DMSO solutions. ¹H NMR titration and other experiments confirm that the sensing process is mainly from the deprotonation of the pyrazole–NH in compound 1.     

Simulation of the (vapor + liquid) equilibria of binary mixtures of benzene,cyclohexane, and hydrogen

Molecular simulations of the (vapor + liquid) equilibria (VLE) for benzene, cyclohexane, and (benzene + hydrogen) and (cyclohexane + hydrogen) were carried out using the Gibbs-ensemble Monte Carlo method with configurational bias. The Buckingham exponential six (exp-6) potential was used for the site–site interactions with no binary interaction parameters; benzene and cyclohexane were described with six interaction sites, and hydrogen with a single site. Simulation results, density, pressure, and vaporization enthalpy for benzene and cyclohexane were in reasonable agreement with experimental data, but critical pressures obtained from extrapolation of the VLE results did not match the experimental values. For (benzene + hydrogen) and (cyclohexane + hydrogen) mixtures mole fractions from simulation were compared with experimental data, the results for liquid phase were in closer agreement with experiment than the results for vapor phase. For the mixtures, results from the PSRK equation of state (PSRK-EOS) predicted the mole fractions for both phases, also vapor densities from molecular simulation were in close agreement with PSRK-EOS. Additionally, the Henry’s law constant (K_H) for hydrogen was calculated in separate simulations using test particle insertions, and qualitative agreement with values from experimental VLE data was obtained. For the (benzene + hydrogen) system K_H results from PSRK-EOS were closer to experiment than the results from simulation, but, for the (cyclohexane + hydrogen) system results from both methods had similar deviations from experiment. The results for pure substance and mixtures indicate that the combination of the three molecular models used for benzene, cyclohexane, and hydrogen is valid for the simulation of the VLE of their mixtures.     

Fluorescence studies on the interaction of hydrophobic ligands with Momordica charantia (bitter gourd) seed lectin

The interaction of Momordica charantia (bitter gourd) seed lectin (MCL) with several nucleic acid bases has been investigated by monitoring changes induced in the protein fluorescence by ligand binding. Values of the binding constant, K_a were obtained as 1.1 × 10⁴, 1.56 × 10⁴ and 2.2 × 10³ M^?1 for adenine, cytosine and uracil, respectively. In addition, binding of 8-anilinonaphthalene 1-sulfonate (ANS) with MCL was investigated by fluorescence spectroscopy. Interaction with MCL at low pH results in a large enhancement of the fluorescence intensity of ANS with a concomitant blue shift in the emission λ_max, whereas at neutral and basic pH changes in both fluorescence intensity and emission maximum were very small, clearly suggesting that the MCL–ANS interaction is stronger at lower pH values. When excited at 295 nm in the presence of ANS, the protein fluorescence decreased with a concomitant increase in the emission intensity of ANS, suggesting resonance energy transfer from the tryptophan residues of MCL to ANS. Gel filtration profiles of MCL at pH values 2.0 and 7.4 are similar indicating that the tetrameric nature of MCL is retained even at low pH. Addition of lactose or adenine to MCL–ANS mixture did not alter the change in ANS fluorescence suggesting that lactose, adenine and ANS bind to MCL at independent and non-interacting sites. These results are relevant to understanding the functional role of MCL in the parent tissue.     

Binding of the bioflavonoid robinetin with model membranes and hemoglobin: Inhibition of lipid peroxidation and protein glycosylation

Recent years have witnessed burgeoning interest in plant flavonoids as novel therapeutic drugs targeting cellular membranes and proteins. Motivated by this scenario, we explored the binding of robinetin (3,7,3′,4′,5′-pentahydroxyflavone, a bioflavonoid with remarkable ‘two color’ intrinsic fluorescence properties), with egg yolk phosphatidylcholine (EYPC) liposomes and normal human hemoglobin (HbA), using steady state and time resolved fluorescence spectroscopy. Distinctive fluorescence signatures obtained for robinetin indicate its partitioning (K_p = 8.65 × 10⁴) into the hydrophobic core of the membrane lipid bilayer. HbA–robinetin interaction was examined using both robinetin fluorescence and flavonoid-induced quenching of the protein tryptophan fluorescence. Specific interaction with HbA was confirmed from three lines of evidence: (a) bimolecular quenching constant K_q ? diffusion controlled limit; (b) closely matched values of Stern–Volmer quenching constant and binding constant; (c) τ₀/τ = 1 (where τ₀ and τ are the unquenched and quenched tryptophan fluorescence lifetimes, respectively). Absorption spectrophotometric assays reveal that robinetin inhibits EYPC membrane lipid peroxidation and HbA glycosylation with high efficiency.     

Pharmacoinformatics study of Piperolactam A from Piper betle root as new lead for non steroidal anti fertility drug development

Fertility control is a burning problem all over the world to regulate population overflow and maintain ecological balance. This study is an in-silico approach to explore a non-steroidal lead as contraceptive agent in order to avoid several contraindications generated by steroidal analogues. Piperolactam A, an aristolactam isolated from Piper betle Linn. showed binding affinity towards estrogen and progesterone receptor as −8.9 and −9.0 Kcal/mol (inhibition constant K_i = 0.294 μM and 0.249 μM) respectively which is even larger than that of reported antagonists such as Rohitukine and OrgC (binding affinity −8.7 and −8.4 Kcal/mol; K_i 0.443 μM and 0.685 μM respectively). The binding site exploration displayed more hydrogen bonding of Piperolactam A (His 524, Leu 346, Thr 347) than Rohitukine and OrgC (Leu 718) with associated receptors which was further confirmed by molecular dynamics simulations. The drug-likeliness of the compound has been proved from its tally with Lipinsky’s Rule of Five and lowered toxicity such as cardiac toxicity, liver toxicity, mutagenicity and ecological toxicity. Endocrine disruptome and later docking guided molecular simulations revealed that Piperolactam A has weaker binding affinity and/or lower probability of binding with nuclear receptors especially hERG and cytochrome P450. The high Caco-2 permeability suggested more bioavailability hence more therapeutic efficacy of the drug.     

Preparation,crystal structure and infrared spectroscopy of the new compound rubidium beryllium sulfate dihydrate,Rb2Be(SO4)2·2H2O

The solubility in the three-component system Rb₂SO₄–BeSO₄–H₂O at 25 °C was studied by the method of isothermal decrease of supersaturation. A new compound, Rb₂Be(SO₄)₂·2H₂O, is formed in a wide concentration range (from solutions containing 27.49 mass% beryllium sulfate and 20.16 mass% rubidium sulfate up to solutions containing 15.08 mass% beryllium sulfate and 39.07 mass% rubidium sulfate).Rb₂Be(SO₄)₂·2H₂O crystallizes in the monoclinic space group P2₁/c (a = 11.371(2) Å, b = 11.858(2) Å, c = 7.431(1) Å, β = 96.33(1), V = 996.0 Å³, Z = 4, R1 = 0.039 for 2672F_o > 4σ(F_o) and 153 variables). The crystal structure is characterized by three-membered chain fragments, composed of a central BeO₂(H₂O)₂ polyhedron sharing corners with two SO₄ tetrahedra. These bent [Be(SO₄)₂(H₂O)₂]²⁻ units are linked by rubidium ions and hydrogen bonds to double layers and further to a three-dimensional framework structure. Rb₂Be(SO₄)₂·2H₂O is isotypic to the respective potassium sulfate and selenate compounds.The strengths of the hydrogen bonds in the title compound as deduced from the infrared wavenumbers of the uncoupled OD stretches of matrix-isolated HDO molecules (isotopically dilute sample) are discussed in terms of the O_w⋯O hydrogen bond distances, the different hydrogen bond acceptor capabilities of the sulfate oxygen atoms and the strong BeOH₂ interactions (synergetic effect). The intramolecular OH bond lengths are derived from the ν_OD versus r_OH correlation curve [H.D. Lutz, C. Jung, J. Mol. Struct. 404 (1997) 63].     

Strain energy of phenanthrene

The strain energy of phenanthrene was derived to be (4.9 ± 2.8) kJ · mol⁻¹, on the basis of the latest standard enthalpies of formation of polycyclic aromatic hydrocarbons. This strain energy agrees well with those estimated from a semi-empirical calculation and from the basicity in hydrogen fluoride solution. The calculation again confirmed the standard enthalpy of formation of phenanthrene, Δ_fH⁰(g)=(201.7±2.9) kJ · mol⁻¹ at T=298.15 K, which was determined by Nagano (J. Chem. Thermodyn. 34 (2002) 377–383). The coupling constant J_4,5 in ¹H-n.m.r. spectrum of phenanthrene in CDCl₃ solution was determined to be 0.55 Hz, which indicates no significant through-space coupling between the 4- and 5-hydrogens.     

Recognition of DNA based on changes in the fluorescence intensity of CdSe/CD QDs–phenanthroline systems

The CdSe quantum dots (QDs) modified by mercapto-β-cyclodextrin (CD) were synthesized and characterized by transmission electron microscopy, powder X-ray diffraction, excitation and emission spectra, and fluorescence lifetime. When λ_ex = 370 nm, the fluorescence peak of CdSe/CD QDs is at 525 nm. Phenanthroline (Phen) is able to quench their fluorescence, which can be recovered by the addition of DNA. The quenching and restoration of fluorescence intensity were found to be linearly proportional to the amount of Phen and DNA, respectively. The variation of the fluorescence intensity of the CdSe/CD QDs–Phen system was studied, and it was demonstrated to result from a static mechanism due to the formation of a Phen inclusion complex with the CdSe QDs modified by mercapto-β-cyclodextrin. The fluorescence recovery was due to the binding of DNA with Phen in the inclusion complex, leading to the freeing of the CdSe/CD QDs. The binding constants and sizes of the binding sites of the Phen–DNA interaction were calculated to be 1.33 × 10⁷ mol^?1 L and 10.79 bp.     

Simultaneous analysis of photoinduced electron transfer in wild type and mutated AppAs

Photoinduced electron transfer (PET) from Tyr21 to isoalloxazine (Iso) in the excited state (Iso*) is considered to be an initial step of the photosensing function of the blue-light sensing using flavin adenine dinucleotide (BLUF) component of the anti-repressor of the photosynthetic regulation (AppA). The PET mechanism was investigated via fluorescence dynamics of AppA and Kakitani and Mataga (KM) theories as well as by molecular dynamic (MD) simulation. The local structures of both the Y21F and W104F mutant AppAs around the Iso binding sites were quite different from those of the wild type (WT) AppA. The distances between Iso and Trp104 in Y21F, and between Iso and Tyr21 in W104F were shorter by 0.06 nm and 0.02 nm, respectively, compared to the WT. The frequency factor, ν₀, in Tyr21 was 1.15-fold greater than that in Trp104. The critical distance between adiabatic and non-adiabatic PET processes, R₀, was found to be very long in the AppA Tyr21. The large values of ν₀ and R₀ for Tyr21 of AppA compared to those in a non photosensing flavoprotein, FMN binding protein (FBP), were elucidated by hydrogen bond (H bond) chain between Tyr21 and Iso through Gln63. Interaction energies among Iso*, Trp104, Tyr21 and Gln63 in WT were calculated using the semi-empirical PM3 method. The amount of the transferred charge from Trp104 to Iso* in the WT exhibited a maximum at an interaction energy of around ?20 kcal/mol, but decreased as the interaction energy (absolute value) increased.     

Studies on the interaction between imidacloprid and human serum albumin: Spectroscopic approach

The interaction between imidacloprid (IMI) and human serum albumin (HSA) was investigated using fluorescence and UV/vis absorption spectroscopy. The experimental results showed that the fluorescence quenching of HSA by IMI was a result of the formation of IMI–HSA complex; static quenching was confirmed to result in the fluorescence quenching. The apparent binding constant K_A between IMI and HSA at three differences were obtained to be 1.51 × 10⁴, 1.58 × 10⁴, and 2.19 × 10⁴ L mol^?1, respectively. The thermodynamic parameters, ΔH° and ΔS° were estimated to be 28.44 kJ mol^?1, 174.76 J mol^?1 K^?1 according to the van’t Hoff equation. Hydrophobic interactions played a major role in stabilizing the complex. The distance r between donor (HSA) and acceptor (IMI) was obtained according to fluorescence resonance energy transfer. The effect of IMI on the conformation of HSA was analyzed using synchronous fluorescence spectroscopy CD and three-dimensional fluorescence spectra, the environment around Trp and Tyr residues were altered.