Band-Gap Energy and Electronic d-d Transitions of NiWO4 Studied under High-Pressure Conditions.

We report an extensive study of the optical and structural properties of NiWO4 combining experiments and density functional theory calculations. We have obtained accurate information on the pressure effect on the crystal structure determining the equation of state and compressibility tensor. We have also determined the pressure dependence of the band gap finding that it decreases under compression because of the contribution of Ni 3d states to the top of the valence band. We report on the sub-band-gap optical spectrum of NiWO4 showing that the five bands observed at 0.95, 1.48, 1.70, 2.40, and 2.70 eV correspond to crystal-field transitions within the 3d8 (t2g6eg2) configuration of Ni2+. Their assignment, which remained controversial until now, has been resolved mainly by their pressure shifts. In addition to the transition energies, their pressure derivatives are different in each band, allowing a clear band assignment. To conclude, we report resistivity and Hall-effect measurements showing that NiWO4 is a p-type semiconductor with a resistivity that decreases as pressure increases.

Pressure-induced order-disorder transitions in ß-In2S3: an experimental and theoretical study of structural and vibrational properties.

This joint experimental and theoretical study of the structural and vibrational properties of ß-In2S3 upon compression shows that this tetragonal defect spinel undergoes two reversible pressure-induced order-disorder transitions up to 20 GPa. We propose that the first high-pressure phase above 5.0 GPa has the cubic defect spinel structure of α-In2S3 and the second high-pressure phase (ϕ-In2S3) above 10.5 GPa has a defect α-NaFeO2-type (R3̄m) structure. This phase, related to the NaCl structure, has not been previously observed in spinels under compression and is related to both the tetradymite structure of topological insulators and to the defect LiTiO2 phase observed at high pressure in other thiospinels. Structural characterization of the three phases shows that α-In2S3 is softer than ß-In2S3 while ϕ-In2S3 is harder than ß-In2S3. Vibrational characterization of the three phases is also provided, and their Raman-active modes are tentatively assigned. Our work shows that the metastable α phase of In2S3 can be accessed not only by high temperature or varying composition, but also by high pressure. On top of that, the pressure-induced ß-α-ϕ sequence of phase transitions evidences that ß-In2S3, a BIII2XV3 compound with an intriguing structure typical of AIIBIII2XVI4 compounds (intermediate between thiospinels and ordered-vacancy compounds) undergoes: (i) a first phase transition at ambient pressure to a disordered spinel-type structure (α-In2S3), isostructural with those found at high pressure and high temperature in other BIII2XV3 compounds; and (ii) a second phase transition to the defect α-NaFeO2-type structure (ϕ-In2S3), a distorted NaCl-type structure that is related to the defect NaCl phase found at high pressure in AIIBIII2XVI4 ordered-vacancy compounds and to the defect LiTiO2-type phase found at high pressure in AIIBIII2XVI4 thiospinels. This result shows that In2S3 (with its intrinsic vacancies) has a similar pressure behaviour to thiospinels and ordered-vacancy compounds of the AIIBIII2XVI4 family, making ß-In2S3 the union link between such families of compounds and showing that group-13 thiospinels have more in common with ordered-vacancy compounds than with oxospinels and thiospinels with transition metals.

Characterization and Decomposition of the Natural van der Waals SnSb2Te4 under Compression.

High pressure X-ray diffraction, Raman scattering, and electrical measurements, together with theoretical calculations, which include the analysis of the topological electron density and electronic localization function, evidence the presence of an isostructural phase transition around 2 GPa, a Fermi resonance around 3.5 GPa, and a pressure-induced decomposition of SnSb2Te4 into the high-pressure phases of its parent binary compounds (α-Sb2Te3 and SnTe) above 7 GPa. The internal polyhedral compressibility, the behavior of the Raman-active modes, the electrical behavior, and the nature of its different bonds under compression have been discussed and compared with their parent binary compounds and with related ternary materials. In this context, the Raman spectrum of SnSb2Te4 exhibits vibrational modes that are associated but forbidden in rocksalt-type SnTe; thus showing a novel way to experimentally observe the forbidden vibrational modes of some compounds. Here, some of the bonds are identified with metavalent bonding, which were already observed in their parent binary compounds. The behavior of SnSb2Te4 is framed within the extended orbital radii map of BA2Te4 compounds, so our results pave the way to understand the pressure behavior and stability ranges of other "natural van der Waals" compounds with similar stoichiometry.

Orpiment under compression: metavalent bonding at high pressure.

We report a joint experimental and theoretical study of the structural, vibrational, and electronic properties of layered monoclinic arsenic sulfide crystals (α-As2S3), aka mineral orpiment, under compression. X-ray diffraction and Raman scattering measurements performed on orpiment samples at high pressure and combined with ab initio calculations have allowed us to determine the equation of state and the tentative assignment of the symmetry of many Raman-active modes of orpiment. From our results, we conclude that no first-order phase transition occurs up to 25 GPa at room temperature; however, compression leads to an isostructural phase transition above 20 GPa. In fact, the As coordination increases from threefold at room pressure to more than fivefold above 20 GPa. This increase in coordination can be understood as the transformation from a solid with covalent bonding to a solid with metavalent bonding at high pressure, which results in a progressive decrease of the electronic and optical bandgap, an increase of the dielectric tensor components and Born effective charges, and a considerable softening of many high-frequency optical modes with increasing pressure. Moreover, we propose that the formation of metavalent bonding at high pressures may also explain the behavior of other group-15 sesquichalcogenides under compression. In fact, our results suggest that group-15 sesquichalcogenides either show metavalent bonding at room pressure or undergo a transition from p-type covalent bonding at room pressure towards metavalent bonding at high pressure, as a precursor towards metallic bonding at very high pressure.

Experimental and Theoretical Study of SbPO4 under Compression.

SbPO4 is a complex monoclinic layered material characterized by a strong activity of the nonbonding lone electron pair (LEP) of Sb. The strong cation LEP leads to the formation of layers piled up along the a axis and linked by weak Sb-O electrostatic interactions. In fact, Sb has 4-fold coordination with O similarly to what occurs with the P-O coordination, despite the large difference in ionic radii and electronegativity between both elements. Here we report a joint experimental and theoretical study of the structural and vibrational properties of SbPO4 at high pressure. We show that SbPO4 is not only one of the most compressible phosphates but also one of the most compressible compounds of the ABO4 family. Moreover, it has a considerable anisotropic compression behavior, with the largest compression occurring along a direction close to the a axis and governed by the compression of the LEP and the weak interlayer Sb-O bonds. The strong compression along the a axis leads to a subtle modification of the monoclinic crystal structure above 3 GPa, leading from a 2D to a 3D material. Moreover, the onset of a reversible pressure-induced phase transition is observed above 9 GPa, which is completed above 20 GPa. We propose that the high-pressure phase is a triclinic distortion of the original monoclinic phase. The understanding of the compression mechanism of SbPO4 can aid to improve the ion intercalation and catalytic properties of this layered compound.

Experimental and Theoretical Studies on α-In2Se3 at High Pressure.

α(R)-In2Se3 has been experimentally and theoretically studied under compression at room temperature by means of X-ray diffraction and Raman scattering measurements as well as by ab initio total-energy and lattice-dynamics calculations. Our study has confirmed the α ( R3 m) → ß' ( C2/ m) → ß ( R3̅ m) sequence of pressure-induced phase transitions and has allowed us to understand the mechanism of the monoclinic C2/ m to rhombohedral R3̅ m phase transition. The monoclinic C2/ m phase enhances its symmetry gradually until a complete transformation to the rhombohedral R3̅ m structure is attained above 10-12 GPa. The second-order character of this transition is the reason for the discordance in previous measurements. The comparison of Raman measurements and lattice-dynamics calculations has allowed us to tentatively assign most of the Raman-active modes of the three phases. The comparison of experimental results and simulations has helped to distinguish between the different phases of In2Se3 and resolve current controversies.

Biological activity and redistribution of nucleolar proteins of two different cell lines treated with cis-dichloro-1,2-propylenediamine-N,N,N',N'-tetraacetato ruthenium (III) (RAP).

The interaction of a newly synthesized antitumor complex cis-dichloro-1,2-propylenediamine-N,N,N',N'-tetraacetato ruthenium (III) (RAP) with DNA was investigated in vitro through a number of techniques including comet assay, immunoprecipitation, and immunolocalization of certain nucleolar proteins (the upstream binding factor (UBF) and fibrillarin) involved in DNA transcription, rRNA processing, and ribosomal assembly. The results showed that RAP binds to the DNA of two cell lines (H4 and Hs-683) causing a delay in cell proliferation rate leading to a number of cellular modifications. These modifications include DNA-damage assessed by the single cell gel electrophoresis method (comet assay) and variation in the expression of nucleolar proteins; UBF was more abundant in RAP treated cells, this was explained by the high affinity of this protein to DNA modified by RAP. On the other hand, fibrillarin was found in less quantities in RAP treated cells which was explained by a de-regulation of the ribosomal machinery caused by RAP.

In vitro expression and redistribution of nucleolar proteins following the treatment with cis-dichloro-1,2-propylenediamine-N,N,N',N'-tetraacetato ruthenium (III) (RAP).

In this study, we used a newly synthesized antitumor complex [RuLCl2]H.4H2O (RAP), having the same antitumor effects as cisplatin but showing lower cytotoxicity. We found that RAP-DNA adducts induce a high expression of proteins with high molecular weight and a low expression of proteins with low molecular weight. We choose two proteins: the upstream binding factor (UBF), an RNA polymerase I-specific transcription factor that recognizes the ribosomal RNA gene promoter and initiates transcription; and fibrillarin, which is involved in many posttranscriptional processes including pre-rRNA processing, pre-rRNA methylation, and ribosome assembly. Our results showed that UBF was present in high quantities in TG cell extracts treated with RAP with a major abundance of UBF1 more than UBF2, which was explained by a high affinity of UBF1 for DNA modified by RAP than UBF2; while fibrillarin was present in low quantities in protein extracts treated with RAP. Also, following treatment with RAP, there was a similar redistribution of UBF along the nucleus of TG cells as in the controls but with the presence of higher quantities of this factor in the nucleoplasm, which could be explained by an increase of the UBF affinity for the no nucleolar chromatin as a consequence of the modifications induced by RAP. Fibrillarin was found in low quantities in the fibrillar centers and in the nucleoplasm after treatment with RAP.

Synthesis, interaction with double-helical DNA and biological activity of the water soluble complex cis-dichloro-1,2-propylenediamine-N,N,N',N'-tetraacetato ruthenium (III) (RAP).

The effects exerted by the new complex cis-dichloro-1,2-propylenediaminetetraacetato ruthenium (III), H[RuCl(2)(PDTA-H(2))] [1, RAP], on DNA and cultured tumor cells (ovarian carcinoma TG cell line) were studied. The comparative study of circular dichroism (CD) spectra obtained from DNA and RAP-DNA system evidences the interaction of the complex with DNA. Compound 1 also interacted with tumor TG cells to slow their proliferation rate. BrdU incorporation was enhanced in cells treated with compound 1, as evidenced by a single-cell electrophoresis method (comet assay), in accordance with RAP-induced DNA damage. DNA migration of compound 1-treated cells was similar to that induced by noxious agents other than cross-linking chemicals. The stability of [RuCl(2)(PDTA-H(2))]-DNA binding is suggested by the high degree of damage that persisted after removal of compound 1 from the culture medium.

Synthesis, structure and biological activity of a new and efficient Cd(II)-uracil derivative complex system for cleavage of DNA.

The new complex formed by Cd(II) and the 1:2 Schiff-base-type ligand 2,6-bis[1-(4-amino-1,2,3,6-tetrahydro-1,3-dimethyl-2,6-dioxopyrimidin-5-yl)imino]ethylpyridine (DAPDAAU) has been chemically and structurally characterized by X-ray diffraction: the ion Cd(II) is surrounded by six nitrogen atoms from two DAPDAAU ligands which coordinates each one in a tridentate fashion through the pyridine ring (N1) and both azomethine nitrogen atoms (N5). The interaction of the Cd(II) complex (compound I) with calf-thymus DNA as observed by circular dichroism spectroscopy suggests the initial unwinding of the DNA double helix strongly depends on increasing incubation times and metal-to-nucleic acid molar ratios. Electrophoretic experiments indicate that the cadmium complex induces cleavage of the plasmid pBR322 DNA to give ulterior nicking and shortening of this molecule, as a result of the complex binding to DNA, resulting in the conclusion that compound I behaves as a chemical nuclease. Cytotoxic activity of the Cd(II) complex against selected different human cancer cell lines is specific and increases with increasing concentration of the metal compound; this fact indicates the potential antitumor character of the complex. When the culture medium is supplemented with compound I, a remarkable inhibition of the growing cell is observed, important cell degeneration appears before 48 h and abundant precipitates are formed that correspond to cell residues and denatured proteins.

Effects of Tris and Hepes buffers on the interaction of palladium-diaminopropane complexes with DNA.

The Pd(II) complexes, [PdCl(2)(1,2-pn)] and [PdCl(2)(1,3-pn)] (pn is diaminopropane), were synthesized and characterized by analytical and spectroscopic (FT-IR, (1)H NMR and (13)C NMR) techniques. UV difference spectral study performed on Pd-pn/DNA systems, indicate a pronounced interaction of palladium complexes with DNA in cell-free media; comparison of lambda(max), Abs(max) and %H values observed for the two compounds might be attributed to structural differences of the chelated ligand rings. Results obtained from electrophoretic analysis of Pd complexes in presence of pBR322 plasmid DNA show a clear decreasing of the supercoiled (SC) DNA form mobility, that could be attributed to unwinding of the double helix; a parallel increasing of the open-circular (OC) DNA form mobility is also noted, this fact implying that the binding of complexes either shortens or condenses the DNA helix. Interaction studies of Pd complexes with plasmid DNA in different buffer systems indicate that DNA binding efficiency capable of modifying the tertiary structure of pBR322 decreased from NaClO(4) to Hepes 2, Hepes 1 [Hepes=4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid], and Tris [(hydroxymethyl)aminomethane] buffers, in this order. Moreover, the level of DNA modifications produced by palladium complexes in 10 mM NaClO(4) remains unchanged after transferring the samples into the medium required for subsequent biophysical or biochemical analyses.

Quantification of isomeric equilibria formed by metal ion complexes of 8-[2-(phosphonomethoxy)ethyl]-8-azaadenine (8,8aPMEA) and 9-[2-(phosphonomethoxy)ethyl]-8-azaadenine (9,8aPMEA). Derivatives of the antiviral nucleotide analogue 9-[2-(phosphonomethoxy)ethyl]adenine (PMEA).

The acidity constants of the two-fold protonated acyclic 9-[2-(phosphonomethoxy)ethyl]-8-azaadenine, H2(9,8aPMEA)(+)(-), and its 8-isomer, 8-[2-(phosphonomethoxy)ethyl]-8-azaadenine, H2(8,8aPMEA)(+)(-), both abbreviated as H2(PA)(+)(-), as well as the stability constants of their M(H;PA)+ and M(PA) complexes with the metal ions M2+=Mg2+, Ca2+, Sr2+, Ba2+, Mn2+, Co2+, Ni2+, Cu2+, Zn2+ or Cd2+, have been determined by potentiometric pH titrations in aqueous solution at I=0.1 M (NaNO3) and 25 degrees C. Application of previously determined straight-line plots of log K(M)M(R-PO3) versus pK(H)H(R-PO3)for simple phosph(on)ate ligands, R-PO3(2-), where R represents a residue without an affinity for metal ions, proves that for all M(PA) complexes a larger stability is observed than is expected for a sole phosphonate coordination of the metal ion. This increased stability is attributed to the formation of five-membered chelates involving the ether oxygen present in the aliphatic residue (-CH2-O-CH2-PO3(2-)) of the ligands. The formation degrees of these chelates were calculated; they vary between about 13% for Ca(8,8aPMEA) and 71% for Cu(8,8aPMEA). The adenine residue has no influence on complex stability except in the Cu(9,8aPMEA) and Zn(9,8aPMEA) systems, where an additional stability increase attributable to the adenine residue is observed and equilibria between four different isomers exist. This means (1) an open isomer with a sole phosphonate coordination, M(PA)op, where PA(2-)=9,8aPMEA2-, (2) an isomer with a five-membered chelate involving the ether oxygen, M(PA)cl/O, (3) an isomer which contains five- and seven-membered chelates formed by coordination of the phosphonate group, the ether oxygen and the N3 site of the adenine residue, M(PA)cl/O/N3, and finally (4) a macrochelated isomer involving N7, M(PA)cl/N7. For Cu(9,8aPMEA) the formation degrees are 15, 30, 48 and 7% for Cu(PA)op, Cu(PA)cl/O, Cu(PA)cl/O/N3 and Cu(PA)cl/N7, respectively; this proves that the macrochelate involving N7 is a minority species. The situation for the Cu(PMEA) system, where PMEA2- represents the parent compound, i.e. the dianion of 9-[2-(phosphonomethoxy)ethyl]adenine, is quite similar. The relationship between the antiviral activity of acyclic nucleoside phosphonates and the structures of the various complexes is discussed and an explanation is offered why 9,8aPMEA is biologically active but 8,8aPMEA is not.

Synthesis, structure, properties and biological behaviour of the complex [RuIV (H2L) Cl2].2H2O (H4L= 1,2-cyclohexanediamminetetraacetic acid).

The highly water-soluble ruthenium complex [Ru(H(2)L)Cl(2)](2)H(2)o, in which H(4)L is the sequestering ligand trans-l, 2-cyclohexanediamminetetraacetic acid (cdta) has been synthesized, structurally characterized and its properties studied. The X-ray crystallographic study shows that the chelating coordinated ligand is tetradentate while the ruthenium environment is octahedral and slightly distorted, with two chloride anions coordinated in cis positions. Potentiometric, conductimetric and infrared studies confirm the presence of two free carboxylic groups, while electronic and voltammetric studies show that the central ion is Ru(IV). The testing of the cytotoxic activity of this complex against three different human cancer cell lines indicates that [Ru(H(2)L)Cl(2)].2H(2)O shows a remarkable and selective antiproliferative effect against the human uterine neck carcinoma HeLa and the malign adenocarcinoma ADLD, showing only a discrete turnout cell inhibition activity against colon adenocarcinoma HT-29. The important antiprotiferative behaviour of complex 1 against the human adenocarcinoma ADLD, indicates that [Ru(H(2)L)Cl(2)].2H(2)O might be considered as potential antineoplastic compound.

Nickel(II), copper(II) and zinc(II) complexes of 9-[2- (phosphonomethoxy)ethyl]-8-azaadenine (9,8aPMEA), the 8-aza derivative of the antiviral nucleotide analogue 9-[2-(phosphonomethoxy)ethyl] adenine (PMEA). Quantification of four isomeric species in aqueous solution.

The acidity constants of the twofold protonated acyclic nucleotide analogue 9-[2-(phosphonomethoxy)- ethyl]-8-azaadenine, H(2)(9,8aPMEA)(+/-), as well as the stability constants of the M(H;9,8aPMEA)(+) and M(9,8aPMEA) complexes with the metal ions M(2+) =Ni(2+), Cu(2+) or Zn(2+), have been determined by potentiometric pH titrations in aqueous solution at I=0.1 M (NaNO(3)) and 25. The result for the release of the first proton from H(2)(9,8aPMEA)(+) (pK(a)= 2.73), which originates from the (N1)H(+) site, was confirmed by UV-spectrophotometric measurements. Application of previously determined straight-line plots of log KMM(R-PO(3)) versus PKH(3)(R-HPO(3))' for simple phosph(on)ate ligands, R- PO-, where R represents a residue without an affinity for metal ions, proves that the primary binding site of 9,8aPMEA(2-) is the phosphonate group for all three metal ions studied. By stability constant comparisons with related ligands it is shown, in agreement with conclusions reached earlier for the Cu(PMEA) system [PMEA(2-)=dianion of 9-[2- (phosphonomethoxy)ethyl]adenine], that in total four different isomers are in equilibrium with each other, i.e. (i) an open isomer with a sole phosphonate coordination, M(PA)(op), where PA(2-)=PMEA(2-)or 9,8aPMEA(2-), (ii) an isomer with a 5-membered chelate involving the ether oxygen, M(PA)cl/o, (iii) an isomer which contains 5- and 7-membered chelates formed by coordination of the phosphonate group, the ether oxygen and the N3 site of the adenine residue, M(PA)(cl/O/N3), and finally (iv) a macrochelated isomer involving N7, M(PA)(cl/]N7). The Cu(2+) systems of PMEA(2-) and 9,8aPMEA(2-) behave quite alike; the formation degrees for Cu(PA)(op), CuM(PA)(cl/O), Cu(PA)(cl/O/N3) and Cu(PA)(cl/N3) are approximately 16, 32, 45 and 7%, respectively, which shows that Cu(PA)(cl/N7) is a minority species. In the Ni(2+) and Zn(2+) systems the open isomer is the dominating one followed by M(PA)(cl/O), but there are indications that the other two isomers also occur to some extent.

Synthesis, characterization, interaction with DNA and cytotoxicity of the new potential antitumour drug cis-K[Ru(eddp)Cl(2)].

The new potential antitumour soluble drug K[Ru(eddp)Cl(2)].3H(2)O, (eddp=ethylenediamine-N,N'-di-3-propionate) has been isolated and characterized. The analysis of the interaction of this complex with pBR322 plasmid DNA by circular dichroism spectroscopy shows that the ruthenium complex initially induces alteration of both CD positive and negative features resembling those previously observed for monofunctional platinum complexes. Further addition of drug at r(i) higher than 0.50 suggests appreciable conformational alterations of typical secondary structure of B-type DNA, implying loss of DNA helicity and unwinding of the double helix. The results reported herein about the binding of K[Ru(eddp)Cl(2)] to the named plasmid performed by electrophoresis indicate that the Ru(III) center preferentially forms initial monofunctional adducts with this plasmid. In addition, the DNA binding data suggest that the plasmid is cleaved by K[Ru(eddp)Cl(2)] in the presence of physiological concentrations of ascorbate. These results support the hypothesis that reactive Ru(II) species may be formed from Ru(III) upon incubation with a reductant agent such as ascorbate. The testing of the cytotoxic activity of this complex against several human cancer cell lines evidenced that K[Ru(eddp)Cl(2)] complex had a remarkable and selective antiproliferative effect against the cervix carcinoma HeLa and colon adenocarcinoma HT-29, behaving in these two cases as an antineoplastic drug.

Study of the biological effects and DNA damage exerted by a new dipalladium-Hmtpo complex on human cancer cells.

The new dipalladium complex [Pd(2)(mu-mtpo-N(3),N(4))(2)(phen)(2)](NO(3))(2) (where phen=1,10-phenantroline; Hmtpo=5,7-dihydro-7-oxo-5-methyl[1,2,4]triazolopyrimidine), (Pd(2)-Hmtpo, or complex I), interacts effectively with DNA plasmid (pBS), as studied by circular dichroism spectroscopy (CD), causing large helix distortions, altering the direction of the main DNA helix axis and producing unwinding of the DNA double helix. DNA damage induced by complex I was highly significant at 2.81 microM (ovarian carcinoma TG cell line), as assessed by comet assay, a dose at which all treated nuclei showed more than 30% DNA migration to the comet tail. DNA damage effect is a consequence of genotoxicity and not a false positive response caused by cytotoxicity. In vitro cytotoxic assay on the two human tumor cell lines TG and BT-20 (breast carcinoma), shows that doses of 0.47, 1.41 and 2.81 microM produce significant antiproliferative effects after 4 days of treatment compared with control. Complex I was highly cytotoxic at 2.81 microM causing an inhibition of viable cells of 65.5%. Cisplatin (cis-DDP) exhibits lower cytotoxic activity in TG cells than dipalladium complex (a cisplatin dose of 6.67 microM inhibits 30.3%) and does not cause migration of DNA to comet tail.