The structure of the extended E2 DNA-binding domain of the bovine papillomavirus-1.

Bovine papillomavirus proteins were extensively studied as a prototype for the human papillomavirus. Here, the crystal structure of the extended E2 DNA-binding domain of the dominant transcription regulator from the bovine papillomavirus strain 1 is described in the space group P31 21. We found two protein functional dimers packed in the asymmetric unit. This new protein arrangement inside the crystal led to the reduction of the mobility of a previously unobserved loop directly involved in the protein-DNA interaction, which was then modeled for the first time.

Morphological and Structural Characterization of (Pt, Au, and Ag) Nanoparticle/Zn-MOF-74 Composites.

Metallic nanoparticles (NPs) were decorated onto Zn-MOF-74 crystals by photoreducing different metal precursors (Pt, Au, and Ag) using ultraviolet (UV) light in an aqueous solution with different metal concentrations without using additional stabilizers. X-ray diffraction revealed the three-dimensional structural integrity and crystallinity conservation of Zn-MOF-74 crystals during the UV decoration process. Raman spectroscopy showed a minor rearrangement in the structure of the Zn-MOF-74 crystal surface after NP decoration. X-ray photoelectron spectroscopy confirmed the metal oxidation states of Zn and NPs. High-resolution transmission electron microscopy images proved the surface decoration of Zn-MOF-74 crystals with spherical metallic NPs with diameters between 2.4 and 9.8 nm.

The structure of the 1H-imidazol-3-ium lawsonate salt aided by ab initio gas-phase calculations.

For the new organic salt 1H-imidazol-3-ium 1,4-dioxo-1,4-dihydronaphthalen-2-olate, C3H5N2(+)·C10H5O3(-), ab initio calculations of the gas-phase structures of the lawsonate and imidazolium ions were performed to help in the interpretation of the structural features observed. Three different types of hydrogen bond are responsible for the three-dimensional packing of the salt.

Hexamethylenetetramine-tridecanedioic acid (1/1): temperature-induced order-disorder structural phase transitions with phase co-existence.

The cocrystal hexamethylenetetramine-tridecanedioic acid (1/1) (HMT-C13), C6H12N4·C13H24O4, was investigated by single-crystal X-ray diffraction techniques at several temperatures during cooling and heating processes. Our results show the formation of two crystalline phases, separated by a large temperature phase co-existence between 290 and 340 K. Phase I, stable above 341 K, presents an orthorhombic structure described in the space group Bmmb, with one N4(CH2)6·C13H22O4 adduct in its asymmetric unit. Phase II, stable below 290 K, presents a monoclinic symmetry described by the space group P21/c, with two N4(CH2)6·C13H22O4 adducts in its asymmetric unit. The phase co-existence is observed both upon cooling and heating, and seems to be related to a complex domain-growth dynamic within the crystal.

Investigation of cobalt(iii)-triazole systems as prototypes for hypoxia-activated drug delivery.

Three novel cobalt(iii)-triazole complexes with structural and redox properties suitable for hypoxia-activated drug delivery were obtained. A major influence of the ancillary ligands (TPA, py2en, py2enMe2) on the electronic properties and reactivity of their complexes was observed. An [O2]-dependent reduction to cobalt(ii) by ascorbic acid provided evidence of hypoxic selectivity.

Superspace crystallography: a key to the chemistry and properties.

An overview is given of the recent advances in the field of modulated molecular and inorganic crystals with an emphasis on the links between incommensurability, intermolecular and interatomic interactions and, wherever possible, the properties of the materials. The importance of detailed knowledge on the modulated structure for understanding the crystal chemistry and the functional properties of modulated phases is shown using selected examples of incommensurate modulations in organic molecular compounds and inorganic complex oxides.

A series of mononuclear Co(III) complexes using tridentate N,O-donor ligands: chemical properties and cytotoxicity activity.

Continuing our interest in tridentate ligands to develop new prototypes of cobalt-based metallodrugs for combating cancer, modifications in the backbone of HL1, [(2-hydroxybenzyl)(2-(pyridil-2-yl)ethyl]amine) were proposed in order to modulate the redox potential of new Co(III) complexes. Three ligands with electron withdrawing groups were synthesized: HL2: [(2-hydroxy-5-nitrobenzyl)(2-(pyridil-2-yl)ethyl]amine); HL3: [(2-hydroxybenzyl)(2-(pyridil-2-yl)ethyl]imine) and HL4: [(2-hydroxy-5-nitrobenzyl)(2-(pyridil-2-yl)ethyl]imine). They were used to obtain the respective mononuclear complexes 2, 3 and 4, which are discussed compared to the previous reported complex 1 (obtained from HL1). The new complexes were characterized and studied by several techniques including X-ray crystallography, elemental and conductimetric analysis, IR, UV-vis and (1)H NMR spectroscopies, and electrochemistry. The substitutions of the group in the para position of the phenol (HL1 and HL2) and the imine instead of the amine (HL3 and HL4), promote anodic shifts in the complexes reduction potentials. The influence of these substitutions in the biological activities of the Co(III) complexes against the murine melanoma cell line (B16F10) was also evaluated. Little effect was observed on cellular viability decrease for all free ligands, however the coordination to Co(III) enhances their activities in the following range: 1>4≈2>3. The data suggest that no straight correlation can be addressed between the reduction potential of the Co(III) center and the cell viability.

Synthesis, characterization and biological activities of mononuclear Co(III) complexes as potential bioreductively activated prodrugs.

Aiming to investigate the use of tridentate ligands to develop new bireductively activated prodrugs, two N(2)O-donor ligands (HL1: [(2-hydroxybenzyl)(2-(imidazol-2-yl)ethyl)]amine; and HL2: [(2-hydroxybenzyl)(2-(pyridil-2-yl)ethyl]amine) were used to synthesize new Co(III) complexes, 1 and 2. Both complexes were characterized by X-ray crystallography, mass spectrometry, electrochemistry, IR, UV-visible and (1)H NMR spectroscopies. Electrochemical data in methanol revealed that the Co(III)-->Co(II) reduction of 1 (-0.84V vs. normal hydrogen electrode - NHE) is more positive than 2 (-1.13V vs. NHE), while it was expected to be more negative due to better sigma-donor ability of imidazole ring in HL1, compared to pyridine in HL2. Considering that reduction processes on Co(III) center may involve the lowest unoccupied molecular orbital (LUMO), it might play an important role on the electronic properties of the complexes, and could explain the observed redox potentials. Then, geometry optimizations of 1 and 2 were performed using the density functional theory (DFT), and different group participation in their LUMO is demonstrated. Using Saccharomyces cerevisiae cells as eukaryotic model, it is shown that in situ generated reduced species, 1(red) and 2(red), have high capacity to inhibit cellular growth, with IC50 (0.50mM for both complexes) lower than cisplatin IC50 (0.6mM) at the same time of exposure. Regarding to their ability to promote S. cerevisiae cells death, after 24 h, cells became susceptible only when exposed to 1(red) and 2(red): (i) at concentrations higher than 0.5mM in a non-dose dependence, and (ii) in anaerobic metabolism. These data reveal the potential of 1 and 2 as bioreductively activated prodrugs, since their oxidized forms do not present expressive activities when compared to their reduced forms.

Structural changes of hexamethylenetetramine and undecanedioic acid co-crystal (HMT-C11) as a function of the temperature.

HMT-C11 belongs to the family of adducts formed by the co-crystallization of N(4)(CH(2))(6) molecules (hexamethylenetetramine or HMT) and aliphatic dicarboxylic acids HOOC(CH(2))(n - 2)COOH with 5

Structural analysis of Tityus serrulatus Ts1 neurotoxin at atomic resolution: insights into interactions with Na+ channels.

The structure of the Ts1 toxin from the Brazilian scorpion Tityus serrulatus was investigated at atomic resolution using X-ray crystallography. Several positively charged niches exist on the Ts1 molecular surface, two of which were found to coordinate phosphate ions present in the crystallization solution. One phosphate ion is bound to the conserved basic Lys1 residue at the Ts1 N-terminus and to residue Asn49. The second ion was found to be caged by residues Lys12, Trp54 and Arg56. Lys12 and Tyr/Trp54 residues are strictly conserved in all classical scorpion beta-neurotoxins. The cavity formed by these residues may represent a special scaffold required for interaction between beta-neurotoxins and sodium channels. The charge distribution on the Ts1 surface and the results of earlier chemical modification studies and side-directed mutagenesis experiments strongly indicate that the phosphate-ion positions mark plausible binding sites to the Na(+) channel. The existence of two distinct binding sites on the Ts1 molecular surface provides an explanation for the competition between Ts1, depressant (LqhIT2) and excitatory (AaHIT) neurotoxins.