A C2-symmetric ratiometric fluorescence and colorimetric anion sensor based on pyrrole derivative

A C₂-symmetric fluorescence and colorimetric anion sensor (1) based on pyrrole derivative was designed and synthesized according to binding site-signaling subunit approach. The compound 1 was easily prepared by reaction of pyrrole-2,5-dicarboxaldehyde with 4-nitrophenylhydrazine in ethanol (yield=78%). In DMSO, the sensor 1 exhibited a visible color change from red to brown upon exposure to anions such as AcO⁻ and F⁻; however, no obvious color changes were observed when the other tested anions (e. g. H₂PO₄⁻, Cl⁻, Br⁻ and I⁻) were added. There was a significant redshift (Δλ_max=160 nm) in UV-vis spectrum during UV-vis spectral titrations. In particular, the sensor 1 showed ratiometric fluorescence responses to anions.     

含酚羟基席夫碱的合成及其阴离子识别

设计和合成一个基于3,5-二叔丁基水杨醛-p-硝基苯腙含酚羟基的新型阴离子受体1. 在加入AcO^-和F^-后,受体1发生从深黄色到紫色的颜色变化. 然而,在加入其它阴离子(H₂PO₄^-, Cl^-, Br^-, I^-)没有明显的颜色变化. 通过紫外和荧光滴定研究了受体与AcO^-和F^-结合的性质.     

基于含偶氮酚羟基席夫碱新型简单比色传感器

通过简单的步骤合成了一个新型的N-(2-羟基-5-氯二苯酮基)-N'-[2-羟基-5-偶氮苯基-苯甲醛]-1,2-二苯胺受体,并有很高的产率．利用紫外光谱研究了受体的阴离子识别的性质．结果表明受体对F^-、AcO^-和H₂PO₄^-有很高的结合能力,而对Cl^-、Br^-和I^-没有结合能力．在受体的二甲基亚砜溶液中加入三种有结合能力的阴离子时,溶液展示了从无色到黄色的明显颜色变化,可以通过裸眼识别．在其它卤素离子存在下受体可以担当氟离子的传感器．紫外数据证明受体与阴离子通过氢键的相互作用形成1:1化学计量比的复合物.     

Optical Recognition of Anions by Ruthenium(II)-Bipyridine-Calix[4]Arene System

The two t-butylcalix[4]arene attached ruthenium(II)-bipyridine complexes (Rubc2 and Rubc3) has been synthesized and the anion recognition studies have been carried out using emission techniques. The binding of anions, which are sensed by the complexes, are studied by UV-visible and emission techniques. The complex Rubc2 recognizes the Cl^?, H₂PO₄ ^? and AcO^? anions. The complex Rubc3 recognizes the Br^? and AcO^? anions. The AcO^? quenches the emission intensity of both two complexes but the other anion increases the emission intensity of the complexes. The excited state lifetime and transient absorption studies were carried out the AcO^? facilitates non radiative pathway. The other anions stabilize the excited state and facilitate the radiative pathway.     

Theory and experiment: Anion binding property of novel phenanthroline or aromatic bridged compounds

A series of artificial compounds, phenanthroline or aromatic bridged indoline derivatives, have been designed and synthesized. The interaction of these compounds with biologically important anions fluoride (F^?), acetate (AcO^?), dihydrogen phosphate (H₂PO₄^?), chloride (Cl^?), bromide (Br^?) and iodide (I^?) was determined by UV–vis, fluorescene titration and theoretical experiments. Results indicate that compound 1 (Di((1″,2″-dihydro-indol-3″-one-2″-hydrazone-1′-hydrazyl)-2′-methylene)-1,3-did-ehydebenzo) and 2 (Di((1″,2″-dihydro-indol-3″-one-2″-hydrazone-1′-hydrazyl)-2′-methylene)-1,3-didehyde-5-nitrobenzo) containing aromatic bridge do not show binding ability for various anions, and that compound 3 (Di((1″,2″-dihydro-indol-3″-one-2″-hydrazone-1′-hydrazyl)-2′-methylene)-2,9-dial-dehyde-1,10-phenanthroline) containing phenanthroline bridge shows the strongest binding ability for F^? among various anions, the moderate binding ability for AcO^? and H₂PO₄^?, and almost no binding ability for Cl^?, Br^?, I^?. The different binding ability of aromatic and phenanthroline bridged compounds may be related to the conjugative effect. What's more, the binding ability of compound 3 with F^? is not interfered by the existence of other anions. Hence, theoretical investigations explore the reasons of different binding ability between compound 3 and anions.     

N-Salicyloyltryptamine: An efficient fluorescent turn-on chemosensor for F and AcO based on an increase in the rigidity of the receptor

The binding abilities of N-salicyloyltryptamine for various anions were investigated by UV-vis, fluorescence and ¹H NMR titration spectra. The obtained results indicated that N-salicyloyltryptamine could selectively recognize biologically important F⁻ and AcO⁻ along with obvious changes in the absorption and emission spectra. Interestingly, addition of F⁻ or AcO⁻ to DMSO solution of N-salicyloyltryptamine caused a notable blueshift and remarkable enhancement in its fluorescence emission spectra.     

A novel colorimetric receptor responding AcO anions based on an azo derivative in DMSO and DMSO/water solution

A novel and efficient receptor based on the phenylhydrazone derivatives is successfully developed and applied to the acetate anion recognition, indicating that the origin of special preference for acetate (AcO⁻) anion maybe the structure well matching between the host and the guest. The sensor changes its color so obviously on addition of the acetate ions and that may make the naked-eye recognition in DMSO and even in DMSO/H₂O (95/5) solution come true. Also, the anion binding ability determinations were performed by UV-vis titration and ¹H NMR titration experiments with different anions in the solutions mentioned. The fluorescence enhancement can also be observed after the host is coordinated with the AcO⁻ anion and excited by light wavelength at 280 nm.     

Design of Two Pyrazole-Based Sensors with Similar Configuration and Different Fluorescent Response to Anions

Two simple fluorescent anion receptors based on 1-phenyl-3-methylpyrozole-5-one-4-one phenylhydrazone (L1) and 1-phenyl-3-methylpyrozole-5-one-4-one p-nitrophenylhydrazone (L2) were designed, synthesized and characterized with ¹H NMR, COSY spectrum, ¹³C NMR, ESI-mass and elemental analyse. Interestingly, two receptors with similar configuration exhibited different anion binding behaviors in DMSO solution. The results of Job plots and ESI-mass spectrum indicate that L1 bind anions such as F⁻, AcO⁻, H₂PO₄⁻ to form 2:1 host-guest complexation, while L2 bind anions to form 1:1 host-guest complexation in the solution.     

Downconversion for the Er, Yb couple in KPb2Cl5—A low-phonon frequency host

Downconversion of a single blue/green photon to two near-infrared photons offers a promising route to increase the efficiency of photovoltaic cells. Here we report on downconversion for the well-known upconversion couple (Er³⁺, Yb³⁺) doped into a host with low (∼200 cm⁻¹) maximum phonon energy (KPb₂Cl₅). The intermediate energy level in both the upconversion and downconversion processes is the ⁴F_7/2 level around 490 nm. While fast multi-phonon relaxation to the lower energy ²H_11/2/⁴S_3/2 levels is beneficial for upconversion, it prevents efficient downconversion. To reduce multi-phonon relaxation, a low-phonon energy host (KPb₂Cl₅) was doped with Er³⁺ and varying amounts of Yb³⁺ co-dopant. The results show that downconversion from the ⁴F_7/2 level occurs, exciting two neighboring Yb³⁺ ions to the ²F_5/2 level. The efficiency is however low due to multi-phonon relaxation from the ⁴F_7/2 to the ⁴S_3/2 level via the intermediate ²H_11/2 level. Based on the results it is clear that efficient downconversion for the (Er³⁺, Yb³⁺) couple requires even lower phonon energy hosts (e.g. bromide host lattices). A Cl⁻-Yb³⁺ charge transfer absorption band is observed between 300 and 400 nm. Excitation in this band results in two broad emission bands centered around 430 and 700 nm at temperatures below 30 K, which are assigned to Cl⁻-Yb³⁺ charge transfer emission.     

Study on the interaction between promethazine hydrochloride and bovine serum albumin by fluorescence spectroscopy

The interaction between promethazine hydrochloride (PMT) and bovine serum albumin (BSA) in vitro was investigated by means of fluorescence spectroscopy and absorption spectroscopy. The fluorescence of BSA was quenched remarkably by PMT and the quenching mechanism was considered as static quenching by forming a complex. The association constants K_a and the number of binding sites n were calculated at different temperatures. The BSA-PMT binding distance was determined to be less than 8 nm, suggesting that energy transfer from BSA to PMT may occur. The thermodynamic parameters of the interaction between PMT and BSA were measured according to the van’t Hoff equation. The enthalpy change (ΔH) and entropy change (ΔS) were calculated to be −23.62 kJ mol⁻¹ and −0.10 J mol⁻¹ K⁻¹, respectively, which indicated that the interaction of PMT with BSA was driven mainly by van der Waals forces and hydrogen bonds. The binding process was a spontaneous process in which Gibbs free energy change (ΔG) was negative. In addition, the results of synchronous fluorescence spectra and three-dimensional fluorescence spectra showed that binding of PMT with BSA can induce conformational changes in BSA.     

Effect of anions on the phase stability of γ-FeOOH nanoparticles and the magnetic properties of gamma-ferric oxide derived from lepidocrocite

The effect of anions such as Cl⁻, SO₄²⁻, and HPO₄²⁻ on the phase stability of FeOOH (α or γ) during precipitation is investigated. Oxidation of Fe(OH)₂·xH₂O from FeCl₂ solution with high Cl⁻ concentration ([Cl⁻]/[Fe]=R_Cl≥8) or (NH₄)₂Fe(SO₄)₂ (FAS) with [HPO₄²⁻]/[Fe]=R_P≥0.02 yields phase-pure γ-FeOOH. In the medium ranges of R_Cl and R_P, mixed phases of α-FeOOH and γ-FeOOH are obtained. Replacement of OH⁻ by Cl⁻ with the bridging cations or strongly bonded HPO₄²⁻ ions in the matrix of the intermediate phase (Fe_x²⁺Fe_y³⁺(OH)_2x+2y−nz·xH₂O(A)_zⁿ⁻, where A is anions such as Cl⁻, SO₄²⁻, HPO₄²⁻, etc.), promoted the lower density γ-FeOOH. However, the particles are less developed and have poor crystallinity as evidenced from transmission electron microscope and thermogravimetry-differential thermal analysis of the precipitates. Whereas, monophasic, uniformly sized, nano-lath shaped particles with high aspect ratio >10 are obtained when morphology-controlling cation additives such as Pt⁴⁺, Pd²⁺ or Rh³⁺ are present in FeCl₂ (R_Cl≥8) solution. Preferential adsorption of additives on (0k0) and (h00) planes limits the growth in the perpendicular directions leading to high aspect ratios. The effect of these additives are suppressed by the phosphate ion, a strong complexing ligand, giving rise to fibrous aggregate with the length of individual particles as small as 10-30 nm. While most of the Cl⁻ ion is removed from the final precipitates on washing, phosphate remained as HPO₄²⁻ as evidenced from IR absorption spectra. Maghemite obtained by dehydroxylating γ-FeOOH contains randomly distributed micropores bringing in the relaxation effects of spins on the surface atoms as deciphered from Mössbauer spectroscopy. This leads to the low σ_s (44-48 emu/g) and H_c (120-130 Oe) for γ-Fe₂O_3−δ particles. Whereas nearly pore-free single crystalline particles obtained by reduction followed by reoxidation has high value of σ_s (73 emu/g) and H_c (320 Oe), which decreases to 30 emu/g and 75 Oe, respectively, for nanoparticles obtained from phosphate stabilized lepidocrocite. The mobility of iron ions and counter mobility of vacancies during the topotactic transformation of γ-FeOOH to magnetite to γ-Fe₂O_3−δ renders the particles pore-free.     

Spectroscopic investigation of Tm:TeO2-WO3 glass

We studied the spectroscopic characteristics of telluride glass with the host composition (0.85)TeO₂-(0.15)WO₃, containing 0.25 and 1.0 mol% thulium oxide (Tm₂O₃). By analyzing the absorption spectra with the Judd-Ofelt theory, the average radiative lifetimes of 305±7.5 μs and 1.95±0.02 ms were determined for the ³F₄ and ³H₄ levels, respectively. Measured fluorescence lifetime of the ³F₄ level decreased from 218 to 51 μs for the 0.25 and 1.0 mol% Tm₂O₃ doped samples, respectively, indicating the effect of boosted non-radiative decay at higher doping concentrations. A similar trend was observed for the ³H₄ level, where the fluorescence lifetime decreased from 1.86 ms to 350 μs at these concentrations. The quenching of the 1460 nm (³F₄→³H₄) emission in favor of the 1800 nm (³H₄→³H₆) emission due to cross relaxation was further evident in the fluorescence spectra of the samples. The calculated stimulated emission cross sections (3.73±0.1×10⁻²¹ cm² at 1460 nm and 6.57±0.07×10⁻²¹ cm² at 1808 nm) reveal the potential importance of the Tm³⁺:(0.85)TeO₂-(0.15)WO₃ glass for applications in fiber-optic amplifiers and fiber lasers.     

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.     

Density functional study of hypophosphite adsorption on Ni (1 1 1) and Cu (1 1 1) surfaces

Surface structures and electronic properties of hypophosphite, H₂PO₂⁻, molecularly adsorbed on Ni(1 1 1) and Cu(1 1 1) surfaces are investigated in this work by density functional theory at B3LYP/6-31++g(d, p) level. We employ a four-metal-atom cluster as the simplified model for the surface and have fully optimized the geometry and orientation of H₂PO₂⁻ on the metal cluster. Six stable orientations have been discovered on both Ni (1 1 1) and Cu (1 1 1) surfaces. The most stable orientation of H₂PO₂⁻ was found to have its two oxygen atoms interact the surface with two PO bonds pointing downward. Results of the Mulliken population analysis showed that the back donation from 3d orbitals of the transition metal substrate to the unfilled 3d orbital of the phosphorus atom in H₂PO₂⁻ and 4s orbital's acceptance of electron donation from one lone pair of the oxygen atom in H₂PO₂⁻ play very important roles in the H₂PO₂⁻ adsorption on the transition metals. The averaged electron configuration of Ni in Ni₄ cluster is 4s^0.634p^0.023d^9.35 and that of Cu in Cu₄ cluster is 4s^1.004p^0.033d^9.97. Because of this subtle difference of electron configuration, the adsorption energy is larger on the Ni surface than on the Cu surface. The amount of charge transfers due to above two donations is larger from H₂PO₂⁻ to the Ni surface than to the Cu surface, leading to a more positively charged P atom in Ni_nH₂PO₂⁻ than in Cu_nH₂PO₂⁻. These results indicate that the phosphorus atom in Ni_nH₂PO₂⁻ complex is easier to be attacked by a nucleophile such as OH⁻ and subsequent oxidation of H₂PO₂⁻ can take place more favorably on Ni substrate than on Cu substrate.     

Tuning Photophysical and Electrochemical Properties of Phosphorescent Heteroleptic Iridium Complex Salts–as Chemosensors

Photophysical and electrochemical studies of cyclometalated cationic heteroleptic iridium(III) complex salts have been carried out. For these complex salts the intense absorption bands appeared around 263 nm and are assigned to spin-allowed π-π* transitions of phenanthroline ligands. Moderately intense and weak absorption bands observed around 341 and 440 nm, respectively. These bands are assigned to spin-allowed metal to ligand charge transfer ¹MLCT and ³MLCT transitions, respectively. The influence of anions and proton on the photophysical and electrochemical studies were also carried out. The emission wavelength was red shifted and emission color changed from yellow to red by the addition of CF₃CO₂H. The solution color changed from green to brown and the emission was quenched by the addition anions such as of F^?, CH₃COO^? and H₂PO₄ ^?.     

Rational Design of Novel Benzimidazole-Based Sensor Molecules that Display Positive and Negative Fluorescence Responses to Anions

Two novel and neutral benzimidazole derivatives-based anion receptors bearing a 1,10-phenanthroline fluorophore, N,N′-di-(2′-benzimidazolyl-methylene)-1, 10-phenanthroline-2,9-diamide (1) and N,N′-di-[2′-(benzimidazolyl-2′-) ethyl-]-1,10-phenanthroline-2,9-diamide (2), which exhibited turn-on and turn-off fluorescence responses to various anions, were rationally designed and synthesized and their fluorescent response toward anions was investigated in DMSO solution. In the process of anions binding, there were two different fluorescent responses in presence of anions: a quenching of the fluorescence emission for F^- and AcO^- and an enhancement of the fluorescence emission for Cl⁻, Br⁻ and I⁻. Two different luminescent mechanisms of the receptors 1 and 2 resulting from various anions were exploited to rationalize quenching and enhancement of the fluorescence emission: a photo-induced electronic transfer mechanism (PET) and the increase of the rigidity of the host molecules, respectively. In particular, chloride could be recognized selectively from the anions tested according to changes of fluorescence spectrum. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Optical properties of lithium magnesium borate glasses doped with Dy and Sm ions

Several studies showed the interesting properties of trivalent lanthanide ions when doped in various types of glasses. Optical and physical properties of lithium magnesium borate glasses doped with Dy³⁺ then with Sm³⁺ ions were determined by measuring their absorption and luminescence spectra in the visible region. The absorption spectra of Dy³⁺ showed eight absorption bands with hypersensitive transition at 1265 nm (⁶H_15/2→⁶F_11/2-⁶H_9/2) and three PL emission bands at 588 nm (⁴F_9/2→⁶H_15/2), 660 nm (⁴F_9/2→⁶H_13/2) and 775 nm (⁴F_9/2→⁶H_11/2). Regarding the Sm3⁺, nine absorption bands were observed with hypersensitive transition at 1237 nm (⁶H_5/2–⁶F_7/2); the PL spectrum showed four prominent peaks at ⁴G_5/2→⁶H_5/2 (yellow color), ⁴G_5/2→⁶H_7/2 (bright orange color), ⁴G_5/2→⁶H_9/2 (orange reddish color) and ⁴G_5/2→⁶H_11/2 (red color), respectively. Finally, a series of physical parameters such as the oscillator strengths, refractive index, ions concentration, Polaron radius and other parameters were calculated for each dopant.     

Dielectric and conductivity relaxations in quaternary ammonium polymer

Ionic conductivity of dry quaternary ammonium polymer, polydiallyldimethylammonium with Cl⁻ and H₂PO₄⁻ counter ions was studied in a wide range of frequencies (10⁻²-10⁷ Hz) and temperatures (300-470 K). The data were analysed within the formalism of permittivity. WAXS, and thermal properties of this polymer were investigated prior to conductivity measurements.     

A turn-on fluorescent anion receptor based on N,N′-di-β-naphthyl-1,10-phenanthroline-2,9-diamide

A simple turn-on fluorescent anion chemosensor with amide moiety as binding sites was designed, synthesized and characterized. Binding ability of the receptor 1 with anions was evaluated through the fluorescence titration in DMSO and the ¹H NMR titration in DMSO-d₆ and coordination of anions to 1 led to a visible enhancement in fluorescence intensity. The fluorescence enhancement could be explained on the basis of two signaling transduction mechanisms: (1) inhibition of a photoinduced electronic transfer (PET) mechanism and (2) anion-induced increase of the rigidity of the host molecules. In addition, the results of ¹H NMR titrations suggested that a host-guest hydrogen-bonding complex with an association constant K_ass=7379 mol⁻¹ L was formed between 1 and F⁻ and the mode of host-guest interactions was provided.     

Effects of Cl, NO3 and SO4 anions on the anodic behavior of carbon steel in deaerated 0.50 M NaHCO3 solutions

The effects of Cl⁻, NO₃⁻ and SO₄²⁻ aggressive anions on the corrosion and passivation behavior of carbon steel electrode in deaerated 0.50 M NaHCO₃ solutions were studied using potentiodynamic anodic polarization and SEM techniques. It was found that the presence of Cl⁻, NO₃⁻ and SO₄²⁻ anions stimulates the anodic dissolution rate in both the active and the pre-passive potential regions. Moreover, significantly great effects were observed in both the passive and the trans-passive potential regions. Pitting corrosion was observed only in the presence of Cl⁻ anions, while the presence of NO₃⁻ and SO₄²⁻ anions facilitate only passivation by oxygen of water without themselves participating in the cathodic process. Also, it was observed that the effect of NO₃⁻ anion, which is a strong oxidizing agent acting “primarily” as stimulator of the cathodic process and then its reaction product acts “indirectly” retarding the anodic process. On the other hand, the effect of SO₄²⁻ anion, which is a non-oxidizing agent, exerts an “indirect” effect on the cathodic reaction increasing its rate and then “directly” influence on the anodic reaction, retarding it.