Novel fluorescent pH sensor based on 5-(4-carboxy-phenyl)-10,15,20-tris(phenyl)-porphyrin

A novel fluorescent pH sensor based on 5-(4-carboxy-phenyl)-10,15,20-tris(phenyl)-porphyrin, as sensing agent, has been developed. The carboxyl functionalized asymmetric porphyrin has been synthesized and characterized by high performance liquid chromatography (HPLC), thin layer chromatography (TLC), proton nuclear magnetic resonance (¹H NMR), Fourier transform infrared spectroscopy (FT-IR), ultraviolet–visible (UV–vis), emission, excitation and mass spectrometry (MS) spectra. Optical and fluorescence behaviors were investigated in relationship with variation of acid concentration in the range of acid pH from 1.5 to 5.5. Upon increasing the acidity of the solution, the decrease of the fluorescence intensity was noticed, as a linear function of pH. Different metal ions were tested to put into evidence the changes regarding the fluorescence intensity, but the fluorescence obtained results revealed no significant interference on pH determination. The conclusion is that the proposed fluorescent sensor can measure pH in acid range in the presence of different metal ions making this sensor a proper one for pH determinations in leaching solutions of the recyclable processes of valuable metals.     

A novel cell-impermeable fluorescent zinc sensor containing poly(ethylene glycol) chain

A novel cell-impermeable zinc sensor was synthesized by incorporating poly（ethylene glycol）（PEG） to N-（8-quinolyl）-p-aminobenzenesulfonamide （HQAS） group.The polymeric zinc sensor combines both valuable features of HQAS and PEG.The HQAS of the sensor has the similar functions to TSQ,and exhibits a good fluorescence response to Zn²⁺ but poor fluorescence responses to other metal ions.The PEG chain can prevent the sensor to permeate healthy cell membrane.The stained experiments with the yeast cells as model showed that the sensor cannot stain the healthy yeast cells,but only the damaged or died yeast cells. These results indicated the novel zinc probe was a typical cell-impermeable zinc sensor.     

p-Dimethylaminobenzaldehyde thiosemicarbazone: a simple novel selective and sensitive fluorescent sensor for mercury(II) in aqueous solution

A novel and simple fluorophore, p-dimethylaminobenzaldehyde thiosemicarbazone (DMABTS), was prepared in order to find available fluorescent chemosensor for mercuric ion in aquesous solution. DMABTS emitted fluorescence at 448 nm in aqueous solution and its fluorescence intensity was completely quenched upon interaction with Hg²⁺ ions, which should be attributed to the 1:1 complex formation between DMABTS and Hg²⁺. The binding constant of the complex was determined as 7.48 × 10⁶ mol l⁻¹. The linear range of quantitative detection of 0 to 5.77 × 10⁻⁶ mol l⁻¹ and the detection limit of 7.7 × 10⁻⁷ mol l⁻¹ for Hg²⁺ in the 6.3 × 10⁻⁶ mol l⁻¹ DMABTS aqueous solution were obtained from a calibration curve. The coexistence of several transition metal ions and anions did interfere the fluorometric titration of Hg²⁺ ion by less than 4% in the emission change.     

A new Ce(III) compound based on 5-aminotetrazole-1-propanoic acid for ablation of HeLa cells

Abstract

Developing new drugs for the treatment of cancer is of great significance. Coordination compounds based on tetrazole-carboxylates are the potential candidates for cancer treatment. In this article, [Ce₂(atzpa)₄(H₂O)₈](NO₃)₂·2H₂O based on 5-aminotetrazole-1-propanoic acid (Hatzpa) and Ce(NO₃)₃·6H₂O has been designed and prepared. Single-crystal X-ray diffraction reveals that the compound is binuclear in which atzpa acts as a bridging ligand. In order to improve the water dispersity of this compound, PEG_-5000 (poly(ethyleneglycol_-5000)) was coated on [Ce₂(atzpa)₄(H₂O)₈](NO₃)₂·2H₂O to prepare the nanoparticles (NPs) in distilled water. In vitro study on HeLa cells shows that Hatzpa is nontoxic itself, while [Ce₂(atzpa)₄(H₂O)₈](NO₃)₂·2H₂O NPs show high toxicity. Such NPs have a low half-inhibitory concentration (IC₅₀) of 24?μg mL^?1 (2.0?×?10^?5 M). In addition, such NPs are able to inhibit the migration of HeLa cells even at a low concentration effectively, showing their potential to inhibit the transfer of tumors in vivo.     

Effect of alkali metal ions on the intrazeolitic migration of Tb(III) ions in zeolite Y

The luminescence spectra of TbLi-Y, TbNa-Y and TbK-Y zeolites treated at different temperatures are reported. It is found that the intrazeolitic migration temperature of Tb(III) ions to hexagonal prisms is influenced by the type of the alkali metal ion present together with Tb(III) to neutralize the negative framework of zeolite Y.     

Preparation, Characterization and Properties of Two New Lanthanide(III)-5-(2-pyridyl)tetrazolate Complexes

Two new mononuclear lanthanide(III) complexes Ln(pytz)3(H2O)3·(H2O)3.5[Ln=Tb(1); Eu(2); Hpytz= 5-(2-pyridyl)tetrazole] were synthesized by reacting Hpytz with the corresponding lanthanide(III) ions and characterized. The single crystal X-ray diffraction analysis reveals that complexes 1 and 2 are isostructural and the lanthanide(III) ions in both complexes 1 and 2 are nine-coordinated, with three oxygen atoms of three coordination water molecules and six nitrogen atoms of three pytz ligands, forming a monocapped square antiprism. Extensive hydrogen bonds exist, resulting in a three-dimensional supramolecular network structure by hydrogen-bonds in both complexes 1 and 2, respectively. Complex 1 exhibits typical green fluorescence of Tb(III) ion and complex 2 red fluorescence of Eu(III) ion, in solid state at room temperature.     

A fluorescent ammonia sensor based on a porphyrin cobalt(II)-dansyl complex

Detecting and measuring the concentration of ammonia is of interest in many scientific and technological areas. A porphyrin based cobalt(II) complex with a dansyl fluorophore has been synthesized and investigated as a ‘turn-on’ fluorescent ammonia sensor. Over sixfold increase in fluorescence emission occurs upon the treatment of NH₃ to [Co(TPP)(Ds-pip)] sensor solution, resulting from NH₃-induced displacement of the axially coordinated fluorophore.     

Complex formation studies on Ho(III) and Lu(III) with 1-(2-pyridylazo)-2-naphthol (PAN) in alcohol-water solutions

The formation ofPAN complexes in the systemsLn(III)—PAN—alcohol-water (where:Ln(III)=Ho, Lu and alcohol=ethanol,n-propanol,iso-propanol) was investigated by a spectrophotometric method. Equilibrium constants for the reactionLn ³⁺ + HLLnL ²⁺ + H⁺ (HL=PAN) and stability constants of complexesLnL ²⁺ were calculated.

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Untersuchungen zur Komplexbildung von Ho(III) und Lu(III) mit 1-(2-Pyridylazo)-2-naphthol (PAN) in alkoholisch-;wä\rigen Lösungen

Zusammenfassung Die Bildung der Komplexe vonPAN in den SystemenLn(III)—PAN—Alkohol-Wasser (Ln(III)=Ho, Lu; Alkohol=Ethanol,n-Propanol,iso-Propanol) wurde mit einer spektrophotometrischen Methode untersucht. Die Gleichgewichtskonstanten der ReaktionenLn ³⁺ + HLLnL ²⁺ + H⁺ (HL==PAN) und die Stabilitätskonstanten der KomplexeLnL ²⁺ wurden berechnet.

     

Photocured thiol-ene based optical fluorescence sensor for determination of gold(III)

This study describes the preparation and the characterization of a new thiol-ene based polymeric fluorescence sensor by photo initiated polymerization of trimethylolpropane tris(3-mercaptopropionate), 2-hydroxyethylacrylate, and 2,4,6-triallyloxy-1,3,5-triazine which are used as monomers and also a photo initiator (2,2-dimethoxy-2-phenylacetophenone) for its usage as optical sensor for gold ions. The thiol-ene based polymeric membrane sensor was characterized by using attenuated total reflectance-fourier transform infrared spectroscopy (ATR-FTIR) and scanning electron microscopy (SEM). The response characteristics of the sensors including dynamic range, pH effect, response time, and the effect of foreign ions were investigated. Fluorescence spectra showed that the excitation/emission maxima of the membrane were at 379/425 nm, respectively     

An ultrasensitive iron(III)-complex based hydrogen peroxide electrochemical sensor based on a nonelectrocatalytic mechanism

In this communication, the first nonelectrocatalysis-type hydrogen peroxide electrochemical sensor is reported. The electroactive iron(III) diethylenetriaminepentaacetic acid (DTPA-Fe^III) complex is immobilized on the cysteamine (cys) modified nanoporous gold (NPG) films by covalent method. The immobilized DTPA-Fe^III complex quickly communicates an electron with the electrode. Upon addition of hydrogen peroxide, however, hydrogen peroxide inhibits the direct electron transfer of the DTPA-Fe^III complex due to the generation of nonelectroactive DTPA-Fe^III–H₂O₂ complex. Based on quenching mechanism, the first hydrogen peroxide electrochemical sensor based on a nonelectrocatalytic mechanism is developed. The novel hydrogen peroxide electrochemical sensor has the ultralow detection limit (1.0 × 10^–14 M) and wide linear range (1.0 × 10^–13 to 1.0 × 10^–8 M) with excellent reproducibility and stability.     

The Study on the Stability Constant and Species Distribution of Eu (III) and Tb (III) Complexes with BDBPH

Biomimetic hydrolysis of DNA or RNA is of increasing importance in biotechnology and medicine. The ability to cleave nucleic acids efficiently, in a non-degradative manner, and with high levels of selectivity for site or structure will be required by many applications for the manipulation of genes, the design of structural probes and the development of novel therapeutics1. There has been much interest in the development of lanthanide complexes as nucleic acid cleavage agents. It has been fou…     

MONO-ORGANOMERCURY AND DIORGANOTHALLIUM DERIVATIVES OF THIOHYDANTOIN AND 5-(BENZYLIDENE)-2-THIOHYDANTOIN: THE CRYSTAL STRUCTURE OF DIMETHYL-[5-(BENZYLIDENE)-2-THIOHYDANTOINATO]-THALLIUM(III)

Abstract

The complexes [TlR₂(Td)], [TlR₂(BTd)], [HgR(Td)] and [HgR(BTd)] (R = Me, Ph; HTd = thiohydantoin; HBTd = 5-(benzylidene)-2-thiohydantoin) were prepared by reacting the appropriate ligand with the appropriate diorganothallium hydroxide or mono-organomercury acetate. They have been studied in the solid state (by vibrational spectroscopy and mass spectrometry) and in solution (by using NMR). In addition, the crystal structure of [TlMe₂(BTd)] has been determined by X-ray diffraction. The crystals have a polymeric structure in which each thallium atom is coordinated to the two methyl C atoms, the S and N atoms of one BTd ligand. the S atom of another and the O atom of a third. The coordination modes of the two ligands in the other complexes are discussed on this basis in the light of spectroscopic data.     

Heteroleptic half-sandwich Ru(II), Rh(III) and Ir(III) complexes based on 5-ferrocenyldipyrromethene

The synthesis and characterization of heteroleptic complexes with the formulations [(η⁶-arene)RuCl(fcdpm)] (η⁶-arene = C₆H₆, C₁₀H₁₄) and [(η⁵-C₅Me₅)MCl(fcdpm)] (M = Rh, Ir; fcdpm = 5-ferrocenyldipyrromethene) have been reported. All the complexes have been characterized by elemental analyses, IR, ¹H NMR and electronic spectral studies. Structures of [(η⁶-C₆H₆)RuCl(fcdpm)] and [(η⁶-C₁₀H₁₄)RuCl(fcdpm)] have been determined crystallographically. Chelating monoanionic linkage of fcdpm to the respective metal centres has been supported by spectral and structural studies. Further, reactivity of the representative complex [(η⁶-C₁₀H₁₄)RuCl(fcdpm)] with ammonium thiocyanate (NH₄SCN) and triphenylphosphine (PPh₃) have been examined.     

Highly sensitive fluorescent sensor targeting CuCl2 based on thiophene attached anthracene compound (TA)

A novel thiophene attached anthracene (TA) based fluorescent compound was designed and synthesized. The TA showed a high quantum yield (Qy = 0.34) in regard to fluorescence. We applied this TA compound to detect specific metal compound and found that it could identify CuCl₂ from other metals through dramatic fluorescence change at λ_max = 460 nm. It showed strong quenching fluorescence property with CuCl₂ while with other metal compounds it exhibited strong blue fluorescence emission. UV/Vis absorption spectroscopy clearly demonstrated that the quenching property of TA at λ_max = 460 nm was due to overlapping of the fluorescence peak of TA at λ_max = 460 nm and the absorption band of CuCl₂ (from 190 nm to 525 nm). Binding constant (K′), which was 0.0895 mM^?2, indicated a complexation ratio between TA and CuCl₂ as 1:2 and this interaction induced quenching property.     

Dual-signaling fluorescent chemosensor based on bisthiazole derivatives

A new bisthiazole chemosensor (3) with phenolic substituents at the position 2 of the thiazole rings was prepared. The chemosensor 3 acts as a potential dual-function fluorescence chemosensor with Cu²⁺ and Zn²⁺ ions causing complete quenching and ratiometric change of fluorescence, respectively. The mechanism of fluorescence was based on the cation-induced inhibition of excited-state intramolecular proton transfer (ESIPT).     

1-Pyrenecarboxaldehyde thiosemicarbazone:A novel fluorescent molecular sensor towards mercury(Ⅱ) ion

<正>A novel and simple fluorescent molecular sensor,1-pyrenecarboxaldehyde thiosemicarbazone(Hpytsc),was synthesized.Its higher sensitivity and selectivity to mercury(Ⅱ) ion were studied through absorption and emission channels.The UV-vis spectra show that the increasing mercury(Ⅱ) ion concentrations result in the decreasing absorption intensity.The fluorescence monomer emission of Hpytsc is enhanced upon binding mercury(Ⅱ) ion,which should be due to the 1:1 complex formation between Hpytsc and metal ion.     

Study on the Fluorescence System of Oxolinic Acid‐Tb(III) and the Determination of Oxolinic Acid

Abstract

In Tris‐HCl buffer (pH=7.43), Tb³⁺ can react with oxolinic acid (OA) and form a 1:2 complex, which emits the intrinsic fluorescence of Tb³⁺. Based on this, a new fluorimetric method of determination of OA is developed. Under the optimum conditions, the enhanced fluorescence intensity of the system is proportional to the concentration of OA in the range of 1.5×10^?7～2.5×10^?5mol/L, and the detection limit is 5.5×10^?9 mol/L. Recovery test was also satisfactory. The experiments indicated that the luminescence mechanism was attributed to the M*–M luminescence.     

Synthesis and anticancer property of one Ce(III) compound based on 5-(2-pyrazinyl)tetrazole-2-acetic acid

Mononuclear [Ce(pztza)₂(H₂O)₆](pztza)·H₂O (1) (pztza = 5-(2-pyrazinyl)tetrazole-2-acetato) has been prepared and characterized by IR, elemental analysis and single-crystal X-ray diffraction. PEG_-5000 (poly(ethyleneglycol_-5000)) coated [Ce(pztza)₂(H₂O)₆](pztza)·H₂O nanoparticles (NPs) can disperse into distilled water. In vitro study on Hela cells shows that Hpztza is nontoxic while [Ce(pztza)₂(H₂O)₆](pztza)·H₂O NPs show high toxicity with half-maximal inhibitory concentration (IC₅₀) of 17 μg/mL (1.93 × 10^?5 M). In addition, such NPs can inhibit the migration of Hela cells effectively.     

Synthesis and Crystal Structure of 4-Bromo-5-ethoxy-3-methyl-5- （naphthalen- 1-yl）- 1-tosyl- 1H-pyrrol-2（5H）- one

The title compound 4-bromo-5-ethoxy-3-methyl-5-(naphthalen-1-yl)-1-tosyl-1H- pyrrol-2(5H)-one 1 (C24H22BrNO4S, Mr = 500.40) has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/n with a = 8.8562(15), b = 18.118(3), c = 14.055(2) , β = 99.855(3)o, V = 2221.9(6) 3, Z = 4, Dc = 1.496 g/cm3, μ = 1.975 mm-1, λ = 0.71073 , F(000) = 1024, R = 0.0607 and wR = 0.1371.