High-Quality Metal-Organic Framework Ultrathin Films for Electronically Active Interfaces.

Currently available methodologies arguably lack the exquisite control required for producing metal-organic framework (MOF) thin films of sufficient quality for electronic applications. By directing MOF transfer with self-assembled monolayers (SAMs), we achieve very smooth, homogeneous, highly oriented, ultrathin films across millimeter-scale areas that display moderate conductivity likely due to electron hopping. Here, the SAM is key for directing the transfer thereby enlarging the number and nature of the substrates of choice. We have exploited this versatility to evolve from deposition onto standard Si and Au to nonconventional substrates such as ferromagnetic Permalloy. We believe that this strategy might be useful for the integration of MOFs as active interfaces in electronic devices.

Unraveling the Decomposition Process of Lead(II) Acetate: Anhydrous Polymorphs, Hydrates, and Byproducts and Room Temperature Phosphorescence.

Lead(II) acetate [Pb(Ac)2, where Ac = acetate group (CH3-COO(-))2] is a very common salt with many and varied uses throughout history. However, only lead(II) acetate trihydrate [Pb(Ac)2·3H2O] has been characterized to date. In this paper, two enantiotropic polymorphs of the anhydrous salt, a novel hydrate [lead(II) acetate hemihydrate: Pb(Ac)2·(1)/2H2O], and two decomposition products [corresponding to two different basic lead(II) acetates: Pb4O(Ac)6 and Pb2O(Ac)2] are reported, with their structures being solved for the first time. The compounds present a variety of molecular arrangements, being 2D or 1D coordination polymers. A thorough thermal analysis, by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), was also carried out to study the behavior and thermal data of the salt and its decomposition process, in inert and oxygenated atmospheres, identifying the phases and byproducts that appear. The complex thermal behavior of lead(II) acetate is now solved, finding the existence of another hydrate, two anhydrous enantiotropic polymorphs, and some byproducts. Moreover, some of them are phosphorescent at room temperature. The compounds were studied by TGA, DSC, X-ray diffraction, and UV-vis spectroscopy.

Homoleptic Iron(II) Complexes with the Ionogenic Ligand 6,6'-Bis(1H-tetrazol-5-yl)-2,2'-bipyridine: Spin Crossover Behavior in a Singular 2D Spin Crossover Coordination Polymer.

Deprotonation of the ionogenic tetradentate ligand 6,6'-bis(1H-tetrazol-5-yl)-2,2'-bipyridine [H2bipy(ttr)2] in the presence of Fe(II) in solution has afforded an anionic mononuclear complex and a neutral two-dimensional coordination polymer formulated as, respectively, NEt3H{Fe[bipy(ttr)2][Hbipy(ttr)2]}·3MeOH (1) and {Fe[bipy(ttr)2]}n (2). The anions [Hbipy(ttr)2](-) and [bipy(ttr)2](2-) embrace the Fe(II) centers defining discrete molecular units 1 with the Fe(II) ion lying in a distorted bisdisphenoid dodecahedron, a rare example of octacoordination in the coordination environment of this cation. The magnetic behavior of 1 shows that the Fe(II) is high-spin, and its Mössbauer spectrum is characterized by a relatively large average quadrupole splitting, ΔEQ = 3.42 mm s(-1). Compound 2 defines a strongly distorted octahedral environment for Fe(II) in which one [bipy(ttr)2](-) anion coordinates the equatorial positions of the Fe(II) center, while the axial positions are occupied by peripheral N-tetrazole atoms of two adjacent {Fe[bipy(ttr)2]}(0) moieties thereby generating an infinite double-layer sheet. Compound 2 undergoes an almost complete spin crossover transition between the high-spin and low-spin states centered at about 221 K characterized by an average variation of enthalpy and entropy ΔH(av) = 8.27 kJ mol(-1), ΔS(av) = 37.5 J K(-1) mol(-1), obtained from calorimetric DSC measurements. Photomagnetic measurements of 2 at 10 K show an almost complete light-induced spin state trapping (LIESST) effect which denotes occurrence of antiferromagnetic coupling between the excited high-spin species and TLIESST = 52 K. The crystal structure of 2 has been investigated in detail at various temperatures and discussed.

Demographic, Social, and Economic Factors of Internalizing Problems in Referred and Non-Referred Adolescents.

Depressive symptoms and suicidal ideation are common internalizing problems during adolescence. Numerous studies have explored the role of certain demographic, social, and economic factors in their development in referred or non-referred adolescents, but not simultaneously in both groups. In this study, we examined the association between age, gender, parents' educational level, and socioeconomic status (SES) and depressive symptoms and suicidal ideation in a referred group (n = 211) and a non-referred (n = 1401) group of adolescents. We also examined the moderating role that these factors play in the relationships between both internalizing problems. The results showed: higher levels of depressive symptoms and suicidal ideation in the referred group; an increase in both problems during early-to-middle adolescence in the non-referred group; an association between low SES and suicidal ideation in both groups; an association between low father's education level and depressive symptoms in the non-referred group; and no gender differences in either of these two internalizing problems. The moderation analyses showed that age, in referred adolescents, and SES, in non-referred adolescents, moderated the relationship between depressive symptoms and suicidal ideation. This study contributes to the identification of groups of vulnerable adolescents that could constitute the target populations of preventive programs.

Influence of processing conditions on acrylamide content in black ripe olives.

The presence of acrylamide was investigated in different presentations of commercial black ripe olives, a well-known sterilized alkali-treated product. The analysis was performed by gas chromatography-mass spectrometry (GC-MS) after bromination of acrylamide, using (13C3)acrylamide as internal standard. In-house validation data for commercial ripe olives showed good precision and accuracy of the method, with repeatability below 3% and recoveries between 94 and 105%. Acrylamide was detected in all samples, but its concentration varied significantly from 176 to 1578 microg/kg of pulp. The effects of different processing conditions (two preservation methods and three darkening methods), cultivar (Hojiblanca or Manzanilla), and presentation form (pitted or sliced olives) on acrylamide content were evaluated in experiments performed in an olive-processing plant. All canned samples were sterilized at 121 degrees C for 30 min. Statistical analysis of the data indicated that the effects of darkening method and olive cultivar were the most pronounced. Acrylamide contents did not significantly differ after 6 months of storage. The small amounts of free amino acids and reducing sugars found in olives before sterilization did not significantly correlate with the acrylamide formed.

Interaction of tocopherols and phenolic compounds with membrane lipid components: evaluation of their antioxidant activity in a liposomal model system.

This paper describes the use of complex liposomes as real membrane models to evaluate the potential benefits of several antioxidants in relation to lipid peroxidation. The xanthine oxidase/Fe(3+)-ADP-EDTA and the Fe(2+)/H2O2 systems have been used to generate hydroxyl radicals and the water soluble azo-compound 2,2'-azobis(2-amidinopropane) dihydrochloride (AAPH) to generate carbon centered radicals (A*) by thermal decomposition. The antioxidant behavior of the rosemary and citrus plant extracts and vitamin-E and vitamin-E acetate alpha-tocopherols have been analyzed. The order of effectiveness in avoiding radical chain reactions has been established by using the colorimetric thiobarbituric acid reaction and the fluorescent probe DPH-PA. ESR spectroscopy has been used to carry out the pursuit of the oxidation processes on the basis of the identification of the radical species resulting from the oxidant system and the ability of the antioxidants to act as scavengers for hydroxyl and AAPH-derived radicals. The modification of the main transition temperature for the lipid mixture and the splitting of the calorimetric peak in the presence of the antioxidants were demonstrated by differential scanning calorimetry. The results obtained showed that the phenols-containing plant extracts and alpha-tocopherols perturb the phase behavior of the BBE lipid bilayer and have a fluidifying effect that could favor the known antioxidant capability and scavenging characteristics of these compounds. 31P-NMR results could be interpreted as, after the incorporation of these antioxidants, those lipid molecules interacting with antioxidants give rise to lamellar phase spectral components with resonance position at lower fields or to isotropic signals in accordance with a higher motion of their phosphate groups.

Solid crystal network of self-assembled cyclodextrin and nonionic surfactant pseudorotaxanes.

The title system allows the straightforward formation of three-dimensional crystals of self-assembled pseudorotaxanes formed by the nonionic surfactant Igepal CO-520 and beta-cyclodextrin (beta-CD) in aqueous solution. The work involves a combination of X-ray powder diffraction, high resolution electron transmission microscopy, and (13)C CP/MAS NMR studies of the solid crystal, supported by single crystal structural analysis. The results indicate a lamellar self-assembly of pseudorotaxanes with preferential orientation and disorder in the structure. For the single crystal, the unit cell was found to be triclinic (P1) and contains a beta-CD dimer. The surfactant molecules are located in the channel formed by these dimers along the c axis of the crystal network. The individual pseudorotaxane structure is formed by a dimer of beta-CDs threaded by the oxyethylene hydrophilic segment of Igepal CO-520, and a beta-CD dimer that binds the hydrophobic region of the surfactant. Thus, as in a CD polyrotaxane structure, this system results in an ordered self-assembly of pseudorotaxanes through the formation of a network of hydrogen bonds between head-to-head beta-CD dimers. Moreover, the analysis of the (1)H NMR spectra in solutions of pseudorotaxanes formed by beta-CD and Igepals with different lengths of the hydrophilic tails indicates equal stoichiometry patterns of both oxyethyelene and hydrophobic regions for the different supramolecules. Whereas the common hydrophobic moiety threads two macrocycles, the ratio between complexed oxyehtlyene segments and beta-CD is 2.5 for the hydrophilic tails. All these results show that nonionic surfactants can be used as alternative and effective linear threads to polymers and copolymers in the synthesis of supramolecular polyrotaxane solid crystals with CDs.

Effect of human papillomavirus on cell cycle-related proteins p16, Ki-67, Cyclin D1, p53, and ProEx C in precursor lesions of cervical carcinoma: a tissue microarray study.

In-depth study of cell cycle proteins and human papillomavirus (HPV) genotyping can provide useful information about the malignant potential of precursor lesions of cervical carcinoma (CC). Immunostaining of cell cycle-related proteins (p16, cyclin D1, Ki-67, p53, and ProEx C) was evaluated using tissue microarrays, and HPV genotypes were identified in 144 cervical tissue specimens encompassing normal or benign epithelial lesions, low- and high-grade squamous intraepithelial lesions (LSIL and HSIL, respectively), and CC. In addition, 14 cases with atypical immature metaplasia (AIM) were included to compare their immunohistochemical features with those of well-established precursor lesions. Expression of p16, Ki-67, and ProEx C was most associated with the severity of dysplasia. Positive expression of p16, Ki-67, and ProEx C and negative expression of p53 seem to be related to HPV-16 infection. AIM cases show an immunohistochemical pattern more similar to LSIL than to HSIL. Immunohistochemical assessment of cell cycle proteins may help to distinguish normal and benign conditions of the cervix from precursor lesions of CC.