Zur chelatometrischen Titration von Blei in Gegenwart von St?relementen

Zusammenfassung Es wurde eine Methode ausgearbeitet, die gestattet, Blei neben zahlreichen Störelementen chelatometrisch zu bestimmen. Triäthanolamin diente bei pH 10 (NH₃/NH₄Cl-Puffer) als Hilfskomplexbildner für Pb. Zur Maskierung der jeweiligen Störelemente wurde Triäthanolamin, Tartrat oder KCN benutzt.Durch Verwendung von 4-(2-Pyridylazo)-resorcin (PAR) als Indicator konnte die Endpunktserkennung gegenüber dem bisher unter ähnlichen Bedingungen benutzten Eriochromschwarz T wesentlich verbessert werden.Blei ist auf diese Weise neben folgenden Elementen mit hoher Genauigkeit zu titrieren: Cu^II, Ni, Zn, Cd, Al, Fe^III, Sn^IV, Sb^III, Bi^III.Alle Titrationen wurden photometrisch durchgeführt. Die relativen Standardabweichungen der einzelnen binären Systeme liegen bei 0,1%.Die meisten Bestimmungen sind auch visuell auszuführen. Der Indicator schlägt von Carminrot nach Reingelb um. Lediglich in Gegenwart von Fe^IIIoder Bi versagt die visuelle Endpunktserkennung, da die Lösung eine Eigenfärbung zeigt bzw. Farbreaktionen mit dem Indicator erfolgen, die den Farbwechsel im Endpunkt verdecken.

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Summary A method is described by which lead can be determined in presence of numerous interfering cations by a chelatometric titration. Triethanolamine is used as an auxiliary complexing agent for lead in an ammoniaammonium chloride buffer at pH 10.Interfering cations may be masked with triethanolamine, tartrate or potassium cyanide. Thus, it is possible to determine lead with high precision in presence of Cu^II, Ni, Zn, Cd, Al, Fe^III, Sn^IV, Sb^III, Bi^III. Substituting Eriochrome Black T by PAR as indicator greatly improves the endpoint in photometric and visual titrations, the latter becoming impossible only in presence of Fe^III and Bi^III, which deteriorate the change of colour at the end point.

     

Coordination chemistry and biological activity of two tridentate ONS and NNS Schiff bases derived from S-benzyldithiocarbazate

Two tridentate Schiff bases having ONS and NNS donor sequences were prepared by condensing S-benzyldithiocarbazate (NH₂NHCSSCH₂Ph) (SBDTC) with pyridine-2-carboxaldehyde and salicylaldehyde, respectively. Complexes of these ligands with Ni^II, Zn^II, Cr^III, Co^II, Cu^II, and Sn^II were studied and characterized by elemental analyses and various physico-chemical techniques. Ni^II, Cu^II, Zn^II and Sn^II complexes were four-coordinate while the Cr^III, Sr^III and Co^III complexes were six-coordinate. The ONS Schiff base was moderately active against leukemia, while its zinc, antimony and cobalt complexes were strongly active against leukemic cells with DC₅₀ = 0.35–5.00.     

Perfectly Encoding π-Conjugated Anions in the RE5(C3N3O3)(OH)12 (RE=Y,Yb, Lu) Family with Strong Second Harmonic Generation Response and Balanced Birefringence

Nonlinear optical (NLO) crystal, which simultaneously exhibits strong second-harmonic-generation (SHG) response and desired optical anisotropy, is a core optical material accessible to the modern optoelectronics. Accompanied by strong SHG effect in a NLO crystal, a contradictory problem of overlarge birefringence is ignored, leading to low frequency doubling efficiency and poor beam quality. Herein, a series of rare earth cyanurates RE₅(C₃N₃O₃)(OH)₁₂ (RE=Y, Yb, Lu) were successfully characterized by 3D electron diffraction technique. Based on a “three birds with one stone” strategy, they enable the simultaneous fulfillment of strong SHG responses (2.5–4.2× KH₂PO₄), short UV cutoff (ca. 220 nm) and applicable birefringence (ca. 0.15 at 800 nm) by the introduction of rare earth coordination control of π-conjugated (C₃N₃O₃)³⁻ anions. These findings provide high-performance short-wavelength NLO materials and highlight the exploration of cyanurates as a new research area.     

Sn2B5O9Cl: A Material with Large Birefringence Enhancement Activated Prepared via Alkaline‐Earth‐Metal Substitution by Tin

The excellent birefringent materials are needed for optical systems. Herein, we reported a new compound, the first tin borate chloride, Sn₂B₅O₉Cl (SBOC) with a large birefringence (0.168 at 546 nm) measured by the polarizing microscope. Its birefringence is 16 times that of the isostructural Ba₂B₅O₉Cl (BBOC) compound (0.010@ at 546 nm). The results show that the birefringence enhancement originates mainly from the Sn²⁺ polyhedra. We propose that the birefringence can be enlarged by substituting the alkaline‐earth metal cation by the Sn²⁺ cation in the isostructural borate with small birefringence. This strategy will guide the discovery of large birefringent materials in the future.     

Perfectly Encoding π-Conjugated Anions in the RE5(C3N3O3)(OH)12 (RE=Y,Yb, Lu) Family with Strong Second Harmonic Generation Response and Balanced Birefringence

Nonlinear optical (NLO) crystal, which simultaneously exhibits strong second-harmonic-generation (SHG) response and desired optical anisotropy, is a core optical material accessible to the modern optoelectronics. Accompanied by strong SHG effect in a NLO crystal, a contradictory problem of overlarge birefringence is ignored, leading to low frequency doubling efficiency and poor beam quality. Herein, a series of rare earth cyanurates RE₅(C₃N₃O₃)(OH)₁₂ (RE=Y, Yb, Lu) were successfully characterized by 3D electron diffraction technique. Based on a “three birds with one stone” strategy, they enable the simultaneous fulfillment of strong SHG responses (2.5–4.2× KH₂PO₄), short UV cutoff (ca. 220 nm) and applicable birefringence (ca. 0.15 at 800 nm) by the introduction of rare earth coordination control of π-conjugated (C₃N₃O₃)³⁻ anions. These findings provide high-performance short-wavelength NLO materials and highlight the exploration of cyanurates as a new research area.     

Chain-like [Sx] (x=2–6) Units Realizing Giant Birefringence with Transparency in the Near-Infrared for Optoelectronic Materials

Birefringent crystals are requisite optical devices in laser and modern opto-electronic fields. Development of excellent birefringent materials is still challenging. Herein, the linear or chain-like [S_x] (x=2–6) species were theoretically proved to be the origin of the large birefringence, and could be regarded as birefringent genes. Besides, the metal polysulfide family was first proposed to be rich birefringent materials source, among which Cs₂S₆ realizes giant birefringence 0.58@1064 nm together with a wide band gap of 1.70 eV (based on the generalized gradient approximation). Moreover, the first dual-anion group polysulfide Na₄Ba₃(S₂)₄S₃ was obtained, showing wide infrared transmission range (0.5–6.2 μm), wide band gap (2.3 eV), and large birefringence (0.37 at 1064 nm). This work provides a new guiding thought for exploring large birefringence crystals in the future.     

Design of the Ionic Organic Nonlinear Optical Material NH4[LiC3H(CH3)O4] with Ultrawide Band Gap and Moderate Birefringence

Ionic organic crystals containing organic planar π-conjugated units has become one of the hot spots as nonlinear optical (NLO) materials. However, although this type of ionic organic NLO crystals commonly have remarkable second harmonic generation (SHG) responses, they also suffer from overlarge birefringences and relatively small band gaps that be hardly beyond 6.2 eV. Herein, a flexible π-conjugated [C₃H(CH₃)O₄]²⁻ unit was theoretically revealed, showing great potential for designing NLO crystals with balanced optical properties. Accordingly, through the reasonable NLO-favourable layered design, a new ionic organic material, NH₄[LiC₃H(CH₃)O₄], was successfully obtained. As expected, it achieves not only a large SHG effect (4×KDP), but also a suitable birefringence (0.06@546 nm) and an ultrawide band gap (>6.5 eV). This study provides a new flexible π-conjugated NLO-active unit, contributing to design more ionic organic NLO materials with excellent balanced optical properties.     

Access to Base Adducts of Low‐Valent Organotin‐Hydride Compounds by Controlled,Stepwise Hydrogen Abstraction from a Tetravalent Organotin Trihydride

Hydrogen can be selectively removed from organotin trihydrides to generate the corresponding organohydrostannylene intermediates. Depending on the size of the substituent and the mode of generation, the intermediates undergo further reactions. Herein, we report on the formation of a variety of organotin hydrides with tin in the oxidation states Sn^II, Sn^I–Sn^III and Sn^III–Sn^III, all accessed by the controlled removal of hydrogen from the tetravalent Ar′Sn^IV trihydride (Ar′=2,6‐dimesitylphenyl, mesityl=2,4,6‐trimethylphenyl).     

Coordination chemistry and biological activity of bidentate and quadridentate nitrogen–sulfur donor ligands and their complexes

The ligand S-benzyldithiocarbazate (SBDTC) acts as a bidentate sulfur–nitrogen chelating agent. The reaction of Sn^II or Sb^III with SBDTC under alkaline conditions gives complexes of composition [Sn(SBDTCA)₂] · 2H₂O and [Sb(SBDTCA)Cl₂ · 2H₂O]. A quadridentate Schiff base of SBDTC with benzil, having a donor sequence SNNS, yields complexes, [Cd(SNNS)] and [Zr(O)(SNNS) · H₂O]. The ligands and the complexes have been characterized by elemental analyses, i.r., u.v.–vis., molar conductance measurements and ¹H-n.m.r. spectroscopy. SBDTC, Sn^II and Sb^III complexes and the SNNS Schiff base together with its Cd^II and Zr^IV complexes display significant antifungal, antibacterial and anti-cancer activity. The Sn^II complex and the SNNS free Schiff base were very effective against Melanoma (skin cancer cells). The SBDTC and its Sn^II complex were also very effective against Renal carcinoma (kidney cancer cells). The results have been compared with those of the uncomplexed metal salts and the free ligands. The minimum concentrations for the evaluation of the above activities for CD₅₀ of the samples were in the 1.0–15 g cm^–3 range.     

Role of Coordination Number and Geometry in Controlling the Magnetic Anisotropy in FeII,CoII, and NiII Single-Ion Magnets

Since the last decade, the focus in the area of single-molecule magnets (SMMs) has been shifting constructively towards the development of single-ion magnets (SIMs) based on transition metals and lanthanides. Although ground-breaking results have been witnessed for Dy^III-based SIMs, significant results have also been obtained for some mononuclear transition metal SIMs. Among others, studies based on Co^II ion are very prominent as they often exhibit high magnetic anisotropy or zero-field splitting parameters and offer a large barrier height for magnetisation reversal. Although Co^II possibly holds the record for having the largest number of zero-field SIMs known for any transition metal ion, controlling the magnetic anisotropy in these systems are is still a challenge. In addition to the modern spectroscopic techniques, theoretical studies, especially ab initio CASSCF/NEVPT2 approaches, have been used to uncover the electronic structure of various Co^II SIMs. In this article, with some selected examples, the aim is to showcase how varying the coordination number from two to eight, and the geometry around the Co^II centre alters the magnetic anisotropy. This offers some design principles for the experimentalists to target new generation SIMs based on the Co^II ion. Additionally, some important Fe^II/Fe^III and Ni^II complexes exhibiting large magnetic anisotropy and SIM properties are also discussed.     

Zero-Birefringence Optical Polymer by Birefringent Crystal and Analysis of the Compensation Mechanism

Summary: We reported a method for compensating the birefringence of optical polymers by doping them with inorganic birefringent crystals. In this method, an inorganic birefringent material is chosen that has the opposite birefringence to the polymer and needle-like shape crystals which are oriented when the polymer chains are oriented. The birefringence of the polymer is thus compensated by the opposing birefringence of the crystal. Orientation behavior of the needle-like crystals and polymers was investigated. The orientation function of the needle-like crystal was increased with an increase in the aspect ratio of the needle-like crystal.     

Birefringence Regulation by Clarifying the Relationship Between Stereochemically Active Lone Pairs and Optical Anisotropy in Tin-based Ternary Halides

It is important to establish and clarify the relationship between stereochemically active lone pairs and birefringence, since it is one of the significantly effective routes to explore birefringent crystals by introducing Sn-centered polyhedra with stereochemically active lone pairs. Herein, four tin(II)-based ternary halides A₃SnCl₅ and ASn₂Cl₅ (A=NH₄ and Rb) have been synthesized successfully. The experimental birefringence of Rb₃SnCl₅ and RbSn₂Cl₅ is larger than or equal to 0.046 and 0.123@546 nm, respectively. Through investigating the alkali or alkaline-earth metal tin(II)-based ternary halides, the structure-performance relationship has been concluded between stereochemically active lone pairs and optical anisotropy. It is beneficial to the analysis and prediction of birefringence in tin-based halides and provides a guide for exploring tin(II)-based optoelectronic functional materials.     

Complexes of a tridentate ONS Schiff base. Synthesis and biological properties

Several new complexes of a tridentate ONS Schiff base derived from the condensation of S-benzyldithiocarbazate with salicylaldehyde have been characterised by elemental analyses, molar conductivity measurements and by i.r. and electronic spectra. The Schiff base (HONSH) behaves as a dinegatively charged ligand coordinating through the thiolo sulphur, the azomethine nitrogen and the hydroxyl oxygen. It forms mono-ligand complexes: [M(ONS)X], [M=Ni^II, Cu^II, Cr^III, Sb^III, Zn^II, Zr^IV or U^VI with X = H₂O, Cl]. The ligand produced a bis-chelated complex of composition [Th(ONS)₂] with Th^IV. Square-planar structures are proposed for the Ni^II and Cu^II complexes. Antimicrobial tests indicate that the Schiff base and five of the metal complexes of Cu^II, Ni^II, U^VI, Zn^II and Sb^III are strongly active against bacteria. Ni^II and Sb^III complexes were the most effective against Pseudomonas aeruginosa (gram negative), while the Cu^II complex proved to be best against Bacillus cereus (gram positive bacteria). Antifungal activities were also noted with the Schiff base and the U^VI complex. These compounds showed positive results against Candida albicans fungi, however, none of them were effective against Aspergillus ochraceous fungi. The Schiff base and its zinc and antimony complexes are strongly active against leukemic cells (CD₅₀ = 2.3–4.3 μg cm⁻³) while the copper, uranium and thorium complexes are moderately active (CD₅₀ = 6.9–9.5 μg cm⁻³). The nickel, zirconium and chromium complexes were found to be inactive. This revised version was published online in June 2006 with corrections to the Cover Date.     

Solvent extraction and spectrophotometric determination of uranium (VI)

Summary Solvent extraction of uranium-sodium diethyldithiocarbamate with ethylmethyl ketone and separation from titanium, zirconium, thorium, lanthanum and cerium has been described. It has been found that 11.75 to 47.00 mg of uranium can be extracted from a binary mixture containing 4.78 to 19.04 mg of titanium, 9.12 to 36.48 mg of zirconium, 116.0 to 460.0 mg of thorium, 6.95 to 27.8 mg of lanthanum or 7.06 to 28.24 mg of cerium at pH 3.0. The pH range between which the separations may be carried out successfully is 2.0 to 3.5. The following cations interfere in the separations: Cu^II, Fe^III, Co^II, Bi^III, Ni^II, Cr^VI, Te^IV, Se^IV, Ag^I, Hg^II, As^III, Sn^IV, Pb^IV, Cd^II, Mo^VI, Mn^II, V^V, Zn^II, In^III, Tl^I, W^VI, Os^VIII and Nb^V.

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Zusammenfassung Uran kann durch Extraktion als Diäthyldithiocarbamidat mit Methyläthylketon von Ti, Zr, Th, La oder Ce getrennt werden. Der günstigste pH-Bereich liegt zwischen 2,0 und 3,5. Die Trennungen wurden mit folgenden Mengen durchgeführt: U (11,75–47,00 mg); Ti (4,78 bis 19,04 mg), Zr (9,12–36,48 mg) Th (116,0–460,0 mg), La (6,95–27,8 mg), Ce (7,06–28,24 mg). Folgende Ionen verursachen Störungen: Cu^II, Fe^III, Co^II, Bi^III, Ni^II, Cr^VI, Te^IV, Se^IV, Ag^I, Hg^II, As^III, Sn^IV, Pb^IV, Cd^II, Mo^VI, Mn^II, V^VI, Zn^II, In^III, Tl^I, W^VI, Os^VIII sowie Nb^V.

     

The photometric determination of Copper by extraction as the Diethyldithiocarbamate. Interferences and their Elimination

Summary Two procedures for the photometric determination of copper as the diethyldithiocarbamate complex have been investigated as to their selectivity.In the first procedure—extraction by chloroform from a citrate solution ofph about 8.5, containing EDTA—the following elements interfere: Hg^II, Ag, Au, Pt, Pd, Os, Sb^III, Te^IV, Tl^III and Bi. Interference by Hg^II, Ag, Pd, Sb^III, Te^IV and Tl^III can be prevented by simple measures.In the second procedure—extraction by a solution of lead diethyldithiocarbamate in chloroform from ammoniacal citrate-only Ag, Tl^III, Bi and Hg^II interfere. Interference by the first three elements can be prevented easily, leaving as the only serious interference in this method mercury in amounts above 500 g.     

Hierarchical Modulation of Optical Anisotropy Driven by Metal Cation Polyhedra in Fluorooxoborates MIIB4O6F2 (MII=Be,Mg, Pb,Zn, Cd)

The enhancement mechanism of birefringence is very important to modulate optical anisotropy and materials design. Herein, the different cations extending from alkaline-earth to alkaline-earth, d¹⁰ electron configuration, and 6s² lone pair cations are highlighted to explore the influence on the birefringence. A flexible fluorooxoborate framework from AEB₄O₆F₂ (AE=Ca, Sr) is adopted for UV/deep-UV birefringent structures, namely, M^IIB₄O₆F₂ (M^II=Be, Mg, Pb, Zn, Cd). The maximal enhancement on birefringence can reach 46.6 % with the cation substitution from Ca, Sr to Be, Mg (route-I), Pb (route-II), and Zn, Cd (route-III). The influence of the cation size, the stereochemically active lone pair, and the binding capability of metal cation polyhedra is investigated for the hierarchical improvement on birefringence. Significantly, the BeB₄O₆F₂ structure features the shortest UV cutoff edge 146 nm among the available anhydrous beryllium borates with birefringence over 0.1 at 1064 nm, and the PbB₄O₆F₂ structure has the shortest UV cutoff edge 194 nm within the reported anhydrous lead borates that hold birefringence larger than 0.1 at 1064 nm. This work sheds light on how metal cation polyhedra modulate birefringence, which suggests a credible design strategy to obtain desirable birefringent structures by cation control.     

Quenching of the luminescence of upconverting luminescent nanoparticles by heavy metal ions

We report that the luminescence of upconverting luminescent nanoparticles (UCLNPs) is quenched by heavy metal ions and halide ions in aqueous solution. The UCLNPs consist of hexagonal NaYF₄ nanocrystals doped with trivalent rare earth ions and were synthesized by both the oleic acid (solvothermal) method and the ethylenediaminetetraacetic acid (co‐precipitation) method. Quenching was studied for the Cu^II, Hg^II, Pb^II, Cd^II, Co^II, Ag^I, Fe^III, Zn^II, bromide, and iodide ions and is found to be particularly strong for Hg^II. Stern–Volmer plots are virtually linear up to quencher concentrations of 10–25 mM , but deviate from linearity at higher quencher concentrations, because static quenching causes an additional effect. The UCLNPs display two main emission bands (blue, green, red or near‐infrared), and the quenching efficiencies for these are found to be different. The effect seems to be generally associated with UCLNPs because it was observed for all UCLNPs doped with trivalent lanthanide ions including Yb^III, Er^III, Ho^III, and Tm^III. The results are discussed in terms of quenching mechanisms and with respect to potential applications such as optical sensing.     

Synthèse et étude structurale d’un nouvel hétéropolytungstate substitué Na8〚H3XIIIMIIW17O59(H2O)〛·36 H2O (X = SbIII,BiIII et M = Mn2+, Co2+, Ni2+, Cu2+, Zn2+) de structure identique à celle de 〚H2XIIIW18O60〛7– (X = As,Bi)

By mixing an aqueous solution of antimonotungstate at pH = 4–5 and an aqueous solution of manganese(II) chloride, of cobalt(II) chloride, of nickel(II) chloride, or of zinc, a monosubstituted heteropolytungstate 〚H₃Sb^IIIM^IIW₁₇O₅₉(H₂O)〛^8– is obtained (M^II = Mn^II, Co^II, Ni^II, Zn^II). The crystallographic study, associated to EPR, XANES, EXAFS, and proton NMR spectrometries, leads to a structure identical to this of 〚H₂As^IIIW₁₈O₆₀〛^7–. There are two moieties Sb^IIIW₉O₃₀ and H₃M^IIW₈O₃₀. It is concluded that the M^II atom substitutes a tungsten atom of the belt of six octahedra perpendicular to the ternary axis of the polytungstate. The same type of compound was obtained starting from bismuth chloride and copper acetate, that is 〚H₃Bi^IIICu^IIW₁₇O₅₉(H₂O)〛^8–.