II ) And Bismuth Research Articles

Effects of copper and bismuth dopants on PVA/NBT film as an X-ray dosimeter

Low-dose X-rays in the order of milligrays (mGy) are employed in diagnostic radiology. This poses a challenge, considering commercially used dosimeters have limitations in detecting low-dose X-rays. Accordingly, the goal of this research was to fabricate a nitro blue tetrazolium-doped polyvinyl alcohol (PVA/NBT) film dosimeter that could respond to low-dose X-rays while also investigating the effects of introducing copper(II) and bismuth(III) ions on the film's detecting ability. The films were synthesized by the solvent casting method and then exposed to X-ray radiation at doses in the range of 0–2.626 mGy. Optical density and UV–Vis transmittance measurements were carried out to identify changes in the film's optical characteristics brought on by X-ray radiation. In addition, changes in the film's surface morphology and chemical structure were examined by scanning electron microscopy (SEM) and FTIR spectroscopy. According to the results of the optical density measurement, introducing copper(II) ions to the film increased its sensitivity and response linearity. In contrast, the opposite was shown in the case of bismuth(III)-doped films. According to FTIR analysis, film X-ray irradiation caused the PVA to degrade. The development of grain structures on the film surface might be related to the reduction of the copper(II) and bismuth(III) ions. This study discovered that copper(II) ion-doped PVA/NBT film has promising low-dose X-ray detection properties.

Thallium(I) Tropolonates: Synthesis, Structure, Spectral Characteristics, and Antimicrobial Activity Compared to Lead(II) and Bismuth(III) Analogues.

Synthesis, single-crystal X-ray determination diffraction and FT-IR, NMR (1H, 13C, 19F and 205Tl), UV–vis, and luminescence spectra characteristics were described for series of thallium(I) compounds: thallium(I) triflate (Tl(OTf)), 1:1 co-crystals of thallium(I) triflate and tropolone (Htrop), Tl(OTf)·Htrop, as well as simple thallium(I) chelates: Tl(trop) (1), Tl(5-metrop) (2), Tl(hino) (3), with Htrop, 5-methyltropolone (5-meHtrop), 4-isopropyltropolone (hinokitiol, Hhino), respectively, and additionally more complex {Tl@[Tl(hino)]6}(OTf) (4) compound. Comparison of their antimicrobial activity with selected lead(II) and bismuth(III) analogs and free ligands showed that only bismuth(III) complexes demonstrated significant antimicrobial activity, from two- to fivefold larger than the free ligands.

Development of a Sensor Based on Poly(1,2‐diaminoanthraquinone) for Individual and Simultaneous Determination of Mercury (II) and Bismuth (III)

AbstractContamination of natural water by mercury (Hg2+) and bismuth (Bi3+) metal ions have been extensively studied due to their toxic effects. A validated square‐wave anodic stripping voltammetry (SW‐ASV) method for determining Bi3+ and Hg2+ ions individually and simultaneously is described. A new electrochemical sensor was constructed using a gold (Au) electrode that has been modified with poly(1,2‐diaminoanthraquinone) (p‐1,2‐DAAQ). Scanning electron microscopy, cyclic voltammetry, and electrochemical impedance spectroscopy were used to characterize the p‐1,2‐DAAQ/Au modified electrode. Factors such as the polymer film thickness, electrolyte, square wave parameters and preconcentration conditions were optimized to improve the performance of the modified Au electrode. Good linear responses were achieved in the concentration ranges of 1–200 μg L−1 and 1–50 μg L−1 forBi3+ and Hg2+, respectively, and the limits of detection were 0.27 μg L−1 (Bi3+) and 0.29 μg L−1 (Hg2+). The interference study results illustrated the high selectivity of the modified electrode for detection of Bi3+ and Hg2+. The proposed SW‐ASV method was successfully applied for Bi3+ and Hg2+analyses in different real water samples.

A Versatile Thin-Film Deposition Method for Multidimensional Semiconducting Bismuth Halides

Despite the significant progress in fabricating hybrid organic–inorganic lead halide perovskite solar cells, their toxicity and low stability remain as major drawbacks, thereby hindering large-scale commercialization. Given the isoelectronic nature of lead(II) and bismuth(III) ions, potentially stable and nontoxic alternatives for efficient light absorption in thin-film photovoltaic (PV) devices may be found among bismuth-based halide semiconductors. However, high-quality polycrystalline films of many of these systems have not been demonstrated. Here we present a versatile and facile two-step coevaporation approach to fabricate A3Bi2I9 (A = Cs, Rb) and AgBi2I7 polycrystalline films with smooth, pinhole-free morphology and average grain size of >200 nm. The process involves an initial two-source evaporation step (involving CsI, RbI or AgI, and BiI3 sources), followed by an annealing step under BiI3 vapor. The structural, optical, and electrical characteristics of the resulting thin films are studied by X-r...

ABOUT THERMAL STABILITY OF BISMUTH(III) IODINE ETIOPORPHYRIN II COMPLEX

For the first time, a complex of bismuth(III) with iodine and etioporphyrin II is reported. It was prepared by reacting etioporphyrin II and bismuth(III) iodide in pyridine in Ar atmosphere. The prepared compound was characterized by FT-IR, 1H-NMR, UV-VIS spectroscopy and mass spectrometry. One intense line at m/z 684.990 attributed to the complex without the iodine atom is observed in the mass spectrum. This is in agreement with the data indicating that bismuthporphyrin complexes generally have low stability. Analysis of FT-IR spectra obtained at room temperature and at 145°С is reported. Priroda15 DFT package was used for optimization of complex geometry and calculation of the IR spectrum. Calculations were done using BPE functional and L1 basis set under relativistic approximation of Dyall Modified Dirac. Assignment of the vibrational frequencies is reported. Collected data indicate that the complex of bismuth(III) with iodine and etioporphyrin II is not stable and easily hydrolyses when exposed to air forming the corresponding hydroxocomplex. This transformation does not change significantly the dynamics of the porphyrin ring.

Tropolone as anionic and neutral ligand in lead(II) and bismuth(III) complexes: Synthesis, structure, characterization and computational studies

Two new metal complexes, [Bi(trop)2(Htrop)(CF3SO3)] (1) and [Pb(trop)2(Htrop)] (2), have been synthesized by reaction of the respective metal triflates with an excess of tropolone (Htrop) in the concentrated methanol or dimethylsulfoxide solution. In addition, it was found that complex 1 crystallizes through the formation of unstable intermediate methanol solvated tris(tropolonato)bismuth(III) compound. The characteristic behavior of tropolone which coordinates both as the bidentate anion (trop−) and the monodentate neutral molecule (Htrop) has been revealed in 1 and 2. The crystal structures of studied compounds have been determined by single-crystal X-ray diffraction. The molecular structures of both complexes have been compared with their geometries received from DFT calculations giving a good correlation. The presented compounds show coordination number of metal ion equal to five in 2 and six in 1 and the presence of stereochemically active 6s2 lone electron pair. The complexes were characterized by FT-IR, NMR and UV–Vis techniques. IR and UV–Vis spectra of 1 and 2 were also simulated by DFT methods. TD-DFT predictions demonstrate the frontier HOMOs and LUMOs cover in the major part the tropolonate and(or) tropolone moieties which gives mainly ligand-to-ligand charge transfer (LLCT) and ligand centered (LC) character to the energy bands above 300 nm.

Investigating the Complexation of the Pb(2+)/Bi(3+) Pair with Dipicolinate Cyclen Ligands.

The complexation properties toward Pb(2+) and Bi(3+) of the macrocyclic ligands 6,6'-((1,4,7,10-tetraazacyclododecane-1,7-diyl)bis(methylene))dipicolinic acid (H2do2pa) and 6,6'-((4,10-dimethyl-1,4,7,10-tetraazacyclododecane-1,7-diyl)bis(methylene))dipicolinic acid (H2Me-do2pa) have been investigated. A new three-step synthesis of H2do2pa following the bisaminal methodology has also been developed. The X-ray structures of [Pb(Me-do2pa)]·6H2O and [Bi(Me-do2pa)](NO3)·H2O show that the two metal ions are eight-coordinated by the ligand. The two complexes exist as the racemic Δ(δδδδ)/Λ(λλλλ) mixture both in the solid state and in solution, as indicated by NMR and DFT studies. The stability constants of the lead(II) and bismuth(III) complexes of the two ligands were determined in 0.5 M KCl using potentiometric and spectrophotometric techniques. The stability constants determined for the complexes of Pb(2+) are relatively high (log KML = 16.44 and 18.44 for H2do2pa and H2Me-do2pa, respectively) and exceptionally high for the complexes of Bi(3+) (log KML = 32.0 and 34.2 for H2do2pa and H2Me-do2pa, respectively). The [Pb(Me-do2pa)] complex presents rather fast formation and very good kinetic inertness toward transchelation. Additionally, the [Bi(Me-do2pa)](+) complex was found to present a remarkably fast complexation rate (full complexation in ∼2 min at pH 5.0, acetate buffer) and a very good kinetic inertness with respect to metal ion dissociation (half-life of 23.9 min in 1 M HCl), showing promise for potential applications in α-radioimmunotherapy.

Metal complexes with 2-acetylpyridine-N(4)-orthochlorophenylthiosemicarbazone: Cytotoxicity and effect on the enzymatic activity of thioredoxin reductase and glutathione reductase

Metal complexes with 2-acetylpyridine-N(4)-orthochlorophenylthiosemicarbazone (H2Ac4oClPh) were assayed for their cytotoxicity against MCF-7 breast adenocarcinoma and HT-29 colon carcinoma cells. The thiosemicarbazone and most of the complexes were highly cytotoxic. H2Ac4oClPh and its gallium(III) and tin(IV) complexes did not show any inhibitory activity against thioredoxin reductase (TrxR) and glutathione reductase (GR). The palladium(II), platinum(II) and bismuth(III) complexes inhibited TrxR at micromolar concentrations but not GR. The antimony(III) and gold(III) complexes strongly inhibited TrxR at submicromolar doses with GR inhibition at higher concentrations. The selectivity of these complexes for TrxR suggests metal binding to a selenol residue in the active site of the enzyme. TrxR inhibition is likely a contributing factor to the mode of action of the gold and antimony derivatives.

ChemInform Abstract: Development of Chiral Catalysts for Mukaiyama Aldol Reactions in Aqueous Media

AbstractReview: [52 refs.

Development of Chiral Catalysts for Mukaiyama Aldol Reactions in Aqueous Media

Since the discovery of the Mukaiyama aldol reaction in 1973, tremendous efforts have been made to develop a definitive catalyst that catalyzes asymmetric Mukaiyama aldol reactions under mild conditions with broad substrate tolerance. Forty years later, an exhaustive search for a water-compatible Lewis acid was able to uncover the hidden potential of iron(II) and bismuth(III), leading to the establishment of broadly applicable and versatile catalytic systems for asymmetric Mukaiyama aldol reactions in aqueous media. The ternary catalytic system was able to expand the substrate generality considerably as the most distinguished catalyst ever reported. The superiority of this methodology over conventional methods has also been demonstrated in terms of high catalytic activity, simplicity of experimental procedures, and a wide substrate range including aqueous aldehydes, for which the stereochemistry had been regarded as difficult to control. Furthermore, a facile synthesis of the chiral ligand underscores its versatility. The reaction did not proceed at all without use of water. In the postulated mechanism, water plays prominent roles in: (1) producing the active metal complexes with a high water-exchange rate constant (3.2 × 10(6)) to activate substrates effectively and to catalyze the reaction through a rapid proton transfer on the order of picoseconds; (2) facilitating the catalytic turnover with simultaneous desilylation as direct access to aldol adducts or facile recovery of active metal complexes; and (3) stabilizing rigid transition states composed of metal complexes and reactants through entropy-driven aggregation derived from the highest cohesive energy density.

Copper(II) and Bismuth(III) Hydroxide Catalyzed Addition Reactions of Hydrazonoester with Allenylboronate in Aqueous Media

Metal-hydroxide-catalyzed addition reactions of hydrazonoester with allenylboronate in aqueous media are described. The propargyl adduct was obtained selectively by using copper(II) hydroxide, whereas the allenyl adduct was produced preferentially using bismuth(III) hydroxide in water―DMF (1:3). The reactions proceeded smoothly in pure water without the use of any organic solvents by addition of a small amount (1.7 mol%) of sucrose.

Extraction chromatographic studies of copper(II) and bismuth(III) with Aliquat-336

A selective method has been developed for extraction chromatographic studies of Cu II and Bi III with Aliquat-336 (liquid anion exchanger) coated on silica gel as a stationary phase. Quantitative extraction of Cu II has been achieved at 4.0-6.0 M HCl and quantitative extraction of Bi III has been achieved at 0.1-4.0 M HCl, 0.1-6.0 M HNO 3 and 1.0-3.0 M H 2 SO 4 . The effects of different acids, stripping agents, flow rate on extraction and elution have been investigated. Cu II and Bi III have been separated from several metal ions. In order to assess the possible analytical application, both the metal ions have been separated from several multicomponent mixtures containing metal ions commonly associated with it. Attempts have been made to extract Cu II from standard alloy and ore samples. The proposed method is simple, rapid and selective.

Electrochemical syntheses and structures of lead(II) and bismuth(III) complexes of 4-(trimethylammonio)benzenethiolate

Two main-group metal complexes of the zwitterionic ammonium thiolate complexes, [M(Tab) 3](ClO 4) n (Tab = 4-(trimethylammonio)benzenethiolate) ( 1: M = Pb, n = 2; 2: M = Bi, n = 3), were prepared by electrochemical oxidation of Pb or Bi electrode in MeCN containing Tab and Et 4NClO 4. Each M atom in 1 and 2 is coordinated by three S atoms of three Tab ligands, forming a trigonal pyramidal coordination geometry. The resulting [M(Tab) 3] n+ cations are interconnected by secondary M⋯S interactions to form two different 1D cationic chains. The electrochemical properties of 1 and 2 were also investigated by cyclic voltammetry.

Tunneling of 6s 2 electrons in PbO and Bi2O3: XANES spectroscopy and DFT calculations

The results of XANES spectroscopy and DFT calculations are evidence for the occurrence of anomalous 2p 2/3→6s 1/2 electronic transitions in lead(II) and bismuth(III) oxides. The observed transitions may be due to the tunneling of outer 6s 2 electrons.

Complexation of macrocyclic ligands with relatively non-solvated metal ions generated in dichloromethane by electrochemical oxidation of amalgam electrodes

Oxidation of a dropping amalgam electrode in dichloromethane (0.2 M Bu 4NPF 6) has been used to examine the complexation of essentially non-solvated cadmium(II), lead(II), thallium(I), tin(II) and bismuth(III) cations with the macrocyclic crown ether 1,4,7,10-tetraoxacyclodecane (12-C-4), the azacrown ether 1,4,8,11-tetraazacyclotetradecane (14-N-4 or cyclam) and the thiacrown ether 1,4,6,11-tetrathiacyclotetradecane (14-S-4) ligands. Interestingly, in dichloromethane, stronger complexes are formed with 14-N-4 and 12-C-4 than with 14-S-4 and the ratio of the ligand to metal ion in the complex is generally larger than the 1:1 value commonly found in other media. The unusual nature of the species formed in dichloromethane is attributed to the highly active nature of the relatively non-solvated cations generated at the amalgam electrode surface.

Lead(II) and Bismuth(III) Complexes with Macrocyclic Ligands

Lead(II) and Bismuth(III) Complexes with Macrocyclic Ligands

Lead(II) and Bismuth(III) Complexes with Macrocyclic Ligands

The preparation and X-ray characterization of a Pb2+ and a Bi3+ complex formed with macrocyclic ligands are reported. In the dimeric complex [{Pb(CH3COO)LBPh4}2], where L is 1,4,7-triazacyclononane, the metal atoms are chelated by L and bridged by an acetate group; moreover, each of the metal atoms is at contact distance from a tetraphenylborate phenyl group, which completes the coordination. The unsymmetrically derivatized macrocycle 1-carboxymethyl-4,7-bis(1-methylimidazol-2-ylmethyl)-1,4,7-triazacyclononane HL1, in its deprotonated (L1, anionic) form gives the complex of formula BiClL1BPh4 with Bi3+, which contains [BiClL1]22+ dimeric cations with eight-coodinated Bi3+ and bridging acetate groups within the dimer.

Copper and Bismuth Complexes Containing Dipyridyl gem-Diolato Ligands: Bi(III)(2)[(2-Py)(2)CO(OH)](2)(O(2)CCF(3))(4)(THF)(2), Cu(II)[(2-Py)(2)CO(OH)](2)(HO(2)CCH(3))(2), and Cu(II)(4)[(2-Py)(2)CO(OH)](2)(O(2)CCH(3))(6)(H(2)O)(2), a Ferromagnetically Coupled Tetranuclear Copper(II) Chain.

The reactions of the singly deprotonated di-2-pyridylmethanediol ligand (dpmdH(-)) with copper(II) and bismuth(III) have been investigated. A new dinuclear bismuth(III) complex Bi(2)(dpmdH)(2)(O(2)CCF(3))(4)(THF)(2), 1, has been obtained by the reaction of BiPh(3) with di-2-pyridyl ketone in the presence of HO(2)CCF(3) in tetrahydrofuran (THF). The reaction of Cu(OCH(3))(2) with di-2-pyridyl ketone, H(2)O, and acetic acid in a 1:2:2:2 ratio yielded a mononuclear complex Cu[(2-Py)(2)CO(OH)](2)(HO(2)CCH(3))(2), 2, while the reaction of Cu(OAC)(2)(H(2)O) with di-2-pyridyl ketone and acetic acid in a 2:1:1 ratio yielded a tetranuclear complex Cu(4)[(2-Py)(2)CO(OH)](2)(O(2)CCH(3))(6)(H(2)O)(2), 3. The structures of these complexes were determined by single-crystal X-ray diffraction analyses. Three different bonding modes of the dpmdH(-) ligand were observed in compounds 1-3. In 2, the dpmdH(-) ligand functions as a tridentate chelate to the copper center and forms a hydrogen bond between the OH group and the noncoordinating HO(2)CCH(3) molecule. In 1 and 3, the dpmdH(-) ligand functions as a bridging ligand to two metal centers through the oxygen atom. The two pyridyl groups of the dpmdH(-) ligand are bound to one bismuth(III) center in 1, while in 3 they are bound two copper(II) centers, respectively. Compound 3 has an unusual one dimensional hydrogen bonded extended structure. The intramolecular magnetic interaction in 3 has been found to be dominated by ferromagnetism. Crystal data: 1, C(38)H(34)N(4)O(14)F(12)Bi(2), triclinic P&onemacr;, a = 11.764(3) Å, b = 11.949(3) Å, c = 9.737(1) Å, alpha =101.36(2) degrees, beta = 105.64(2) degrees, gamma = 63.79(2) degrees, Z = 1; 2, C(26)H(26)N(4)O(8)Cu/CH(2)Cl(2), monoclinic C2/c, a = 25.51(3) Å, b = 7.861(7) Å, c = 16.24(2) Å, beta = 113.08(9) degrees, Z = 4; 3, C(34)H(40)N(4)O(18)Cu(4)/CH(2)Cl(2), triclinic P&onemacr;, a = 10.494(2) Å, b = 13.885(2) Å, c = 7.900(4) Å, alpha =106.52(2) degrees, beta = 90.85(3) degrees, gamma = 94.12(1) degrees, Z = 1.

Extraction, Separation, and Determination of Nickel and Bismuth with 1-(2-Pyridylazo)-2-naphthol in Aqueous Thiocyanate Media

Abstract Nickel(II) and bismuth(III) are quantitatively extracted from aqueous thiocyanate solutions, adjusted to pH 4.0–9.0 and 3.5–5.0, respectively, using solutions of 1-(2-pyridylazo)-2-naphthol (PAN) in tri-n-butyl phosphate (TBP). The extracted species of nickel and bismuth have the formulas [Ni(PAN)SCN]·4TBP and [Bi(PAN)SCN]X·TBP, respectively. Polyurethane foam treated with TBP solution containing PAN is used successfully for the quantitative retention and recovery of nickel and bismuth from aqueous thiocyanate solutions in the column extraction mode. The preconcentration of small amounts (10 mg) of nickel and bismuth from dilute aqueous solutions (1 L) is also possible, with a recovery of 95–97%. The feasibility of using PAN-foam for selective detection and semiquantitative determination of nickel and bismuth in aqueous thiocyanate media is examined. The detection limits of nickel and bismuth by the foam batch method are 0.05 and 0.50 ppm, respectively. Lower concentrations of these metal ions ar...

1,3,5-Triamino-1,3,5-trideoxy-cis-inositol, a new ligand with a remarkable versatility for metal ions. 4. Preparation, characterization, and x-ray structure of the trinuclear lead(II) and bismuth(III) complexes

Three compounds, containing the complexes [Pb 3 (H -3 taci)] 3+ (taci=1,3,5-triamino-1,3,5-trideoxy-cis-inositol), have been prepared by combining solutions of taci and the corresponding metal nitrates. Single-crystal X-ray analysis of Pb 6 (H -3 taci) 2 (NO 3 ) 5 (OH)(H 2 O) 2 , P1 and Bi 3 (H -3 taci) 2 Cl 3 -6H 2 O, R3, revealed the presence of trinuclear complexes, where each metal ion is bound to one terminal amino group and to two deprotonated, bridging hydroxyl groups of taci.