Manolis J. Manos

Layered Metal Sulfides Capture Uranium from Seawater

Uranium is the main source for nuclear energy but also one of the most toxic heavy metals. The current methods for uranium removal from water present limitations, such as narrow pH operating range, limited tolerance to high salt concentrations, or/and high cost. We show here that a layered sulfide ion exchanger K(2)MnSn(2)S(6) (KMS-1) overcomes these limitations and is exceptionally capable in selectively and rapidly sequestering high (ppm) as well as trace (ppb) quantities of UO(2)(2+) under a variety of conditions, including seawater. KMS-1 can efficiently absorb the naturally occurring U traces in seawater samples. The results presented here reveal the exceptional potential of sulfide-based ion-exchangers for remediating of uranium-containing wastes and groundwater and for extracting uranium from the sea.

Layered metal sulfides: Exceptionally selective agents for radioactive strontium removal

In this article, we report the family of robust layered sulfides K2xMnxSn3-xS6 (x = 0.5–0.95) (KMS-1). These materials feature hexagonal [MnxSn3-xS6]2x− slabs of the CdI2 type and contain highly mobile K+ ions in their interlayer space that are easily exchangeable with other cations and particularly strontium. KMS-1 display outstanding preference for strontium ions in highly alkaline solutions containing extremely large excess of sodium cations as well as in acidic environment where most alternative adsorbents with oxygen ligands are nearly inactive. The implication of these results is that simple layered sulfides should be considered for the efficient remediation of certain nuclear wastes.

Turn‐On Luminescence Sensing and Real‐Time Detection of Traces of Water in Organic Solvents by a Flexible Metal–Organic Framework

The development of efficient sensors for the determination of the water content in organic solvents is highly desirable for a number of chemical industries. Presented herein is a Mg(2+) metal-organic framework (MOF), which exhibits the remarkable capability to rapidly detect traces of water (0.05-5 % v/v) in various organic solvents through an unusual turn-on luminescence sensing mechanism. The extraordinary sensitivity and fast response of this MOF for water, and its reusability make it one of the most powerful water sensors known.

Highly Efficient and Rapid Cs+ Uptake by the Layered Metal Sulfide K2xMnxSn3−xS6 (KMS-1)

The details of the ion-exchange properties of the layered sulfide material K(2x)Mn(x)Sn(3-x)S(6) (x = 0.5-0.95) (KMS-1) with Cs(+) and Rb(+) cations are reported. X-ray photoelectron spectroscopy (XPS), elemental analyses, and powder and single-crystal diffraction studies revealed that the Cs(+) and Rb(+) ion exchange of KMS-1 is complete (quantitative replacement of K(+) ions) and topotactic. These data also revealed that the Cs(+) exchange is accompanied with a rare topotactic oxidation of Mn(2+) to Mn(3+) caused by atmospheric oxygen, while the Rb(+) ion exchange only slightly alters the oxidation state of the layer manganese atoms. The absorption of Cs(+) by KMS-1 follows the Langmuir model with a high exchange capacity of 226(4) mg/g (pH approximately 7) and distribution coefficients as high as 2 x 10(4) mL/g. KMS-1 displays significant cesium uptake both under strongly acidic (pH 0.7-2.6) or basic conditions (pH 10-12). The kinetics of Cs(+) capture by KMS-1 is fast (>90% removal of approximately 1 ppm of Cs(+) within only 5 min). KMS-1 was also found capable to efficiently absorb Cs(+) from complex solutions containing various competitive cations in large excess. KMS-1 (containing Mn(3+) ions) can be regenerated and reused for Cs(+) exchange with an exchange capacity very similar to that of the pristine KMS-1. The results indicate that layered metal sulfides with ion-exchange properties may be considered as highly selective and cost-effective sorbents for remediation of water contaminated with the radioactive (137)Cs isotope. The selectivity over other alkali ions for Cs originates not from a size effect but from the more favorable Cs...S soft Lewis acid/Lewis base interactions.

Sequestration of Heavy Metals from Water with Layered Metal Sulfides

Extraordinarily effective heavy metal ion scavenger: We show here that the material K(2x)Mn(x)Sn(3-x)S(6) (x = 0.5-0.95) (KMS-1) overcomes the limitations of the known heavy metal ion sorbents, showing the capability to rapidly reduce the concentrations of Cd, Hg, and Pb ions well-below the legally acceptable levels for drinking water. KMS-1 is inexpensive, easily prepared in large quantities, and may play a role in addressing the global problem of water contamination with heavy metal ions. The paradigm of heavy metal ion absorption of KMS-1 is the ability to form very strong M-S bonds.

Use of Hydrazine in the Hydrothermal Synthesis of Chalcogenides: the Neutral Framework Material [Mn2SnS4(N2H4)2]

The reaction system Mn/Sn/S/hydrazine/water at approximately 150 degrees C afforded [Mn(2)SnS(4)(N(2)H(4))(2)] (1). The compound has a unique neutral three-dimensional framework with bridging hydrazine ligands and a variety of interconnectivity modes between MnL(6) (L = N, S) octahedra. The complex structure of 1 leads to strong antiferromagnetic interactions between the Mn(2+) centers and ordering at approximately 41 K. The stabilization of 1 underscores the high potential of hydrazine to promote the formation of novel chalcogenide materials under solvothermal conditions.

Structural Motifs and Biological Studies of New Antimony(III) Iodide Complexes with Thiones

Eight new antimony(III) iodide complexes of the heterocyclic thioamides, 2-mercapto-1-methylimidazole (MMI), 2-mercaptobenzimidazole (MBZIM), 5-ethoxy-2-mercaptobenzimidazole (EtMBZIM), 2-mercaptothiazolidine (MTZD), 3-methyl-2-mercaptobenzothiazole (NMeMBZT), 2-mercapto-3,4,5,6-tetrahydropyrimidine (tHPMT), 2-mercaptopyridine (PYT), and 2-mercaptopyrimidine (PMT) of formulas {[SbI(3)(MMI)(2)].MeOH} (1), [SbI(3)(MBZIM)(2)] (2), {[SbI(2)(mu(2)-I)(EtMBZIM)(2)](2).H(2)O} (3), [SbI(3)(MTZD)] (4), [(NMeMBZT)SbI(2)(mu(2)-I)(2)(mu(2)-S-NMeMBZT)SbI(2) (NMeMBZT)] (5), {[SbI(3)(tHPMT)(3)].MeOH} (6), [SbI(3)(PYT)] (7), and [SbI(3)(PMT)(2)] (8), have been synthesized and characterized by elemental analysis, FT-IR spectroscopy, FT-Raman spectroscopy, and TG-DTA analysis. The crystal structures of 3, 4, 5, 6, and 7 were also determined by X-ray diffraction. The complexes show interesting structural motifs. Complex 6 is a monomer, with octahedral (Oh) geometry around the metal ion formed by three sulfur and three iodide atoms. Complexes 3 and 5 are dimers, with a square pyramidal (SP) geometry in each monomeric unit, while complexes 4 and 7 are polymers with pseudotrigonal bipyramidal (psi-TBP). Two or three sulfur atoms from thioamide ligands and three iodide atoms are bound to Sb atoms forming building blocks for the dimers and polymers. Strong intramolecular interactions between mu(2)-I and/or mu(2)-S and Sb atoms stabilize both structures. In dimer complex 5, two terminal iodide and one terminal sulfur atom are bonded to the Sb ion, while two mu(2)-I and one mu(2)-S bridging atoms bridge the metal ions forming psi-Oh geometry. Computational studies using multivariant linear regression (MLR) and artificial neural networks (ANN) and considering biological results (50% inhibitory concentration, IC(50)) as dependent variables derived a theoretical equation for IC(50) values of the complexes studied. The calculated IC(50) values are compared satisfactorily with the experimental inhibitory activity of the complexes measured. Complexes 3-7 were used to study their influence upon the catalytic peroxidation of linoleic acid by the enzyme Lipoxygenase (LOX). Compounds 1-8 were also tested for in vitro cytotoxicity, and they showed mostly a moderate cytostatic activity against a variety of tumor cell lines but comparable with those found for the antimony(III) chloride and bromide complexes, reported earlier [Ozturk et al. Inorg. Chem. 2007, 46, 2861-2866; Ozturk et al. Inorg. Chem. 2009, 48, 2233-2245].

Polyoxomolybdenum(V) Sulfite Complexes: Synthesis, Structural, and Physical Studies†

Reaction of Na2MoVIO4·2H2O with (NH4)2SO3 in the mixed-solvent system H2O/CH3CN (pH = 5) resulted in the formation of the tetranuclear cluster (NH4)4[Mo4VISO16]·H2O (1), while the same reaction in ...

Insertion of Functional Groups into a Nd3+ Metal–Organic Framework via Single-Crystal-to-Single-Crystal Coordinating Solvent Exchange

Single-crystal-to-single-crystal (SCSC) transformations represent some of the most fascinating phenomena in chemistry. They are not only intriguing from a basic science point of view but also provide a means to modify or tune the properties of the materials via the postsynthetic introduction of suitable guest molecules or organic functional groups into their structures. Here, we describe UCY-2, a new flexible Nd(3+) metal-organic framework (MOF), which exhibits a unique capability to undergo a plethora of SCSC transformations with some of them being very uncommon. These structural alterations involve the replacement of coordinating solvent molecules of UCY-2 by terminally ligating solvents and organic ligands with multiple functional groups including -OH, -SH, -NH-, and -NH(2) or their combinations, chelating ligands, anions, and two different organic compounds. The SCSC coordinating solvent exchange is thus demonstrated as a powerful method for the functionalization of MOFs.

Synthesis, structural characterization and in vitro inhibitory studies against human breast cancer of the bis-(2,6-di-tert-butylphenol)tin(IV) dichloride and its complexes

Four new organotin(IV) complexes of bis-(2,6-di-tert-butylphenol)tin(IV) dichloride [(tert-Bu-)(2)(HO-Ph)](2)SnCl(2) (1) with the heterocyclic thioamides 2-mercapto-pyrimidine (PMTH), 2-mercapto-4-methyl-pyrimidine (MPMTH), 2-mercapto-pyridine (PYTH) and 2-mercapto-benzothiazole (MBZTH), of formulae {[(tert-Bu-)(2)(HO-Ph)](2)Sn(PMT)(2)} (2), {[(tert-Bu-)(2)(HO-Ph)](2)Sn(MPMT)(2)} (3), {[(tert-Bu-)(2)(HO-Ph)](2)SnCl(PYT)} (4) and {[(tert-Bu-)(2)(HO-Ph)](2)SnCl(MBZT)} (5), have been synthesized and characterized by elemental analysis, (1)H-, (13)C-, (119)Sn-NMR, EPR, FT-IR, Raman and Mössbauer spectroscopic techniques. The crystal and molecular structures of compounds 1–5 have been determined by X-ray diffraction. The geometries around the metal center adopted in complexes 1–5 varied between tetrahedral in 1, trigonal bipyramidal in 3, 4, 5 and distorted octahedral in 2. Two carbon atoms from aryl groups and two chlorine atoms form a distorted tetrahedron in the case of 1. Two carbon, two sulfur and two nitrogen atoms from thione ligands form a distorted octahedral geometry around tin(IV) with trans-C(2), cis-N(2), cis-S(2)-configurations in 2. However, in the case of 4 and 5 complexes two carbon, one sulfur, one nitrogen and one chloride atom form a distorted trigonal bipyramidal arrangement. Finally, in the case of 3 the trigonal bipyramidal geometry is achieved by two carbon, two sulfur and one nitrogen atom in a unique coordination mode of thioamides toward the tin(IV) cation. Compounds 1–5 were tested for their in vitro cytotoxicity against the human breast adenocarcinoma (MCF-7) cell line. Compound 3 exhibits strong cytotoxic activity against MCF-7 cells (IC(50) = 0.58 ± 0.1 μM).