(2E)-3-(4-Ethoxyphenyl)-1-(2-methyl-4-phenylquinolin-3-yl)prop-2-en-1-on e monohydrate

The title hydrate, C27H23NO2 center dot H2O, features an almost planar quinoline residue (r.m.s. deviation = 0.015 angstrom) with the benzene dihedral angle = 63.80 (7)degrees] and chalcone C-C-C-O torsion angle = -103.38 (18)degrees] substituents twisted significantly out of its plane. The configuration about the C=C bond 1.340 (2) angstrom] is E. In the crystal, molecules related by the 21 symmetry operation are linked along the b axis via water molecules that form O-H center dot center dot center dot O-c and O-H center dot center dot center dot N-q hydrogen bonds (c = carbonyl and q = quinoline). A C-H center dot center dot center dot O interaction also occurs.

Identification of collagenolytic MMP networks as potential biomarkers in progressive chronic periodontitis subjects and MMP-8 null allele model

Chronic periodontitis results from a complex aetiology, including the formation of a subgingival biofilm and the elicitation of the host s immune and inflammatory response. The hallmark of chronic periodontitis is alveolar bone loss and soft periodontal tissue destruction. Evidence supports that periodontitis progresses in dynamic states of exacerbation and remission or quiescence. The major clinical approach to identify disease progression is the tolerance method, based on sequential probing. Collagen degradation is one of the key events in periodontal destructive lesions. Matrix metalloproteinase (MMP)-8 and MMP-13 are the primary collagenolytic MMPs that are associated with the severity of periodontal inflammation and disease, either by a direct breakdown of the collagenised matrix or by the processing of non-matrix bioactive substrates. Despite the numerous host mediators that have been proposed as potential biomarkers for chronic periodontitis, they reflect inflammation rather than the loss of periodontal attachment. The aim of the present study was to determine the key molecular MMP-8 and -13 interactions in gingival crevicular fluid (GCF) and gingival tissue from progressive periodontitis lesions and MMP-8 null allele mouse model. In study (I), GCF and gingival biopsies from active and inactive sites of chronic periodontitis patients, which were determined clinically by the tolerance method, and healthy GCF were analysed for MMP-13 and tissue inhibitor of matrix metalloproteinases (TIMP)-1. Chronic periodontitis was characterised by increased MMP-13 levels and the active sites showed a tendency of decreased TIMP-1 levels associated with increments of MMP-13 and total protein concentration compared to inactive sites. In study (II), we investigated whether MMP-13 activity was associated with TIMP-1, bone collagen breakdown through ICTP levels, as well as the activation rate of MMP-9 in destructive lesions. The active sites demonstrated increased GCF ICTP levels as well as lowered TIMP-1 detection along with elevated MMP-13 activity. MMP-9 activation rate was enhanced by MMP-13 in diseased gingival tissue. In study (III), we analysed the potential association between the levels, molecular forms, isoenzyme distribution and degree of activation of MMP-8, MMP-14, MPO and the inhibitor TIMP-1 in GCF from periodontitis progressive patients at baseline and after periodontal therapy. A positive correlation was found for MPO/MMP-8 and their levels associated with progression episodes and treatment response. Because MMP-8 is activated by hypochlorous acid in vitro, our results suggested an interaction between the MPO oxidative pathway and MMP-8 activation in GCF. Finally, in study (IV), on the basis of the previous finding that MMP-8-deficient mice showed impaired neutrophil responses and severe alveolar bone loss, we aimed to characterise the detection patterns of LIX/CXCL5, SDF-1/CXCL12 and RANKL in P. gingivalis-induced experimental periodontitis and in the MMP-8-/- murine model. The detection of neutrophil-chemoattractant LIX/CXCL5 was restricted to the oral-periodontal interface and its levels were reduced in infected MMP-8 null mice vs. wild type mice, whereas the detection of SDF-1/CXCL12 and RANKL in periodontal tissues increased in experimentally-induced periodontitis, irrespectively from the genotype. Accordingly, MMP-8 might regulate LIX/CXCL5 levels by undetermined mechanisms, and SDF-1/CXCL12 and RANKL might promote the development and/or progression of periodontitis.

Molecular structure of Lantadene-B&C, triterpenoids ofantana camara, red variety: Lantadene-B, 22β-angeloyloxy-3-oxoolean-12-en-28-oic acid; Lantadene-C, 22 β-(S)-2′-methyl butanoyloxy-3-oxoolean-12-en-28-oic acid

(I)Lantadene-B: C35H52O5,M r =552.80, MonoclinicC2,a=25.65(1),b=6.819(9),c=18.75(1) Å,beta=100.61(9),V=3223(5) Å3,Z=4,D x =1.14 g cm–3 CuKagr (lambda=1.5418A),mgr=5.5 cm–1,F(000)=1208,R=0.118,wR=0.132 for 1527 observed reflections withF o ge2sgr(F o ). (II)Lantadene-C: C35H54O5·CH3OH,Mr=586.85, Monoclinic,P21,a=9.822(3),b=10.909(3),c=16.120(8)Å,beta=99.82(4),V=1702(1)Å3,Z=2,D x =1.145 g cm–3, MoKagr (lambda=0.7107Å), mgr=0.708 cm–1 F(000)=644,R=0.098, wR=0.094 for 1073 observed reflections. The rings A, B, C, D, and E aretrans, trans, trans, cis fused and are in chair, chair, sofa, half-chair, chair conformations, respectively, in both the structures. In the unit cell the molecules are stabilized by O-HctdotO hydrogen bonds in both the structures, however an additional C-HctdotO interaction is observed in the case of Lantadene-C.

Production of Carcinogenic Acetaldehyde by Oral Microbiome

Oral cancer is the seventh most common cancer worldwide and its incidence is increasing. The most important risk factors for oral cancer are chronic alcohol consumption and tobacco smoking, up to 80 % of oral carcinomas are estimated to be caused by alcohol and tobacco. They both trigger an increased level of salivary acetaldehyde, during and after consumption, which is believed to lead to carcinogenesis. Acetaldehyde has multiple mutagenic features and it has recently been classified as a Group 1 carcinogen for humans by the International Agency for Research on Cancer. Acetaldehyde is metabolized from ethanol by microbes of oral microbiota. Some oral microbes possess alcohol dehydrogenase enzyme (ADH) activity, which is the main enzyme in acetaldehyde production. Many microbes are also capable of acetaldehyde production via alcohol fermentation from glucose. However, metabolism of ethanol into acetaldehyde leads to production of high levels of this carcinogen. Acetaldehyde is found in saliva during and after alcohol consumption. In fact, rather low ethanol concentrations (2-20mM) derived from blood to saliva are enough for microbial acetaldehyde production. The high acetaldehyde levels in saliva after alcohol challenge are explained by the lack of oral microbiota and mucosa to detoxify acetaldehyde by metabolizing it into acetate and acetyl coenzymeA. The aim of this thesis project was to specify the role of oral microbes in the in vitro production of acetaldehyde in the presence of ethanol. In addition, it was sought to establish whether microbial metabolism could also produce acetaldehyde from glucose. Furthermore, the potential of xylitol to inhibit ethanol metabolism and acetaldehyde production was explored. Isolates of oral microbes were used in the first three studies. Acetaldehyde production was analyzed after ethanol, glucose and fructose incubation with gas chromatography measurement. In studies I and III, the ADH enzyme activity of some microbes was measured by fluorescence. The effect of xylitol was analyzed by incubating microbes with ethanol and xylitol. The fourth study was made ex vivo and microbial samples obtained from different patient groups were analyzed. This work has demonstrated that isolates of oral microbiota are able to produce acetaldehyde in the presence of clinically relevant ethanol and glucose concentrations. Significant differences were found between microbial species and isolates from different patient groups. In particular, the ability of candidal isolates from APECED patients to produce significantly more acetaldehyde in glucose incubation compared to healthy and cancer patient isolates is an interesting observation. Moreover, xylitol was found to reduce their acetaldehyde production significantly. Significant ADH enzyme activity was found in the analyzed high acetaldehyde producing streptococci and candida isolates. In addition, xylitol was found to reduce the ADH enzyme activity of C. albicans. Some results from the ex vivo study were controversial, since acetaldehyde production did not correlate as expected with the amount of microbes in the samples. Nevertheless, the samples isolated from patients did produce significant amounts of acetaldehyde with a clinically relevant ethanol concentration.

Interaction of nitrogen and oxygen with C60

Evidence is presented for the strong interaction of nitrogen and oxygen with buckminsterfullerene.

Interaction of A beta peptide (1-40) with amino acid aluminium complexes: relevance to Alzheimer's disease

A beta (39-43 aminoacid residues) is the principal peptide component of amyloid deposits in Alzheimer's disease (AD). A beta peptide is derived from the amyloid precursor protein (APP) in which mutations give rise to many forms of familial AD. Aluminium is reported to play a key role in inducing conformational change in the synthetic beta-amyloid peptide (1-40)from alpha-helix to beta-pleated sheet, leading to aggregation and fibrillar formation. We have studied the interaction of amino acid-Al complexes such as D-Asp-Al and L-Glu-Al with A beta(1-40) in TFE/buffer (70% TFE and 30% H2O v/v pH 6.7) mixture using CD spectroscopy. The interaction of either of these amino acid complexes with A beta(1-40) results in loss of alpha-helical content and the peptide is more unstructured compared to free Al3+ in the solution. Our data strongly support the idea, that the Al3+ in the form of aminoacid-Al complexes is more effective in inducing random coil conformation in the A beta peptide than the free Al3+ present in the solution.

Interaction anisotropy and shear instability of aspirin polymorphs established by nanoindentation

Nanoindentation is applied to the two polymorphs of aspirin to examine and differentiate their interaction anisotropy and shear instability. Aspirin provides an excellent test system for the technique because: (i) polymorphs I and II exhibit structural similarity in two dimensions, thereby facilitating clear examination of the differences in mechanical response in relation to well-defined differences between the two crystal structures; (ii) single crystals of the metastable polymorph II have only recently become accessible; (iii) shear instability has been proposed for II. Different elastic moduli and hardness values determined for the two polymorphs are correlated with their crystal structures, and the interpretation is supported by measured thermal expansion coefficients. The stress-induced transformation of the metastable polymorph II to the stable polymorph I can be brought about rapidly by mechanical milling, and proceeds via a slip mechanism. This work establishes that nanoindentation provides ``signature'' responses for the two aspirin polymorphs, despite their very similar crystal structures. It also demonstrates the value of the technique to quantify stability relationships and phase transformations in molecular crystals, enabling a deeper understanding of polymorphism in the context of crystal engineering.

Direct evidence of redox interaction between metal ion and support oxide in Ce(0.98)Pd(0.02)O(2-delta) by a combined electrochemical and XPS study

A combined electrochemical method and X-ray photo electron spectroscopy (XPS) has been utilized to understand the Pd(2+)/CeO(2) interaction in Ce(1-x)Pd(x)O(2-delta) (x = 0.02). A constant positive potential (chronoamperometry) is applied to Ce(0.98)Pd(0.02)O(2-delta) working electrode which causes Ce(4+) to reduce to Ce(3+) to the extent of similar to 35%, while Pd remains in the +2 oxidation state. Electrochemically cycling this electrode between 0.0-1.2 V reverts back to the original state of the catalyst. This reversibility is attributed to the reversible reduction of Ce(4+) to Ce(3+) state. CeO(2) electrode with no metal component reduces to CeO(2-y) (y similar to 0.4) after applying 1.2 V which is not reversible and the original composition of CeO(2) cannot be brought back in any electrochemical condition. During the electro-catalytic oxygen evolution reaction at a constant 1.2 V for 1000 s, Ce(0.98)Pd(0.02)O(2-delta) reaches a steady state composition with Pd in the +2 states and Ce(4+) : Ce(3+) in the ratio of 0.65 : 0.35. This composition can be denoted as Ce(0.63)(4+)Ce(0.35)(4+)Pd(0.02)O(2-delta-y) (y similar to 0.17). When pure CeO(2) is put under similar electrochemical condition, it never reaches the steady state composition and reduces almost to 85%. Thus, Ce(0.98)Pd(0.02)O(2-delta) forms a stable electrode for the electro-oxidation of H(2)O to O(2) unlike CeO(2) due to the metal support interaction.

The interaction of halogen molecules with SWNTs and graphene

The interaction of halogen molecules of varying electron affinity, such as iodine monochloride (ICl), bromine (Br(2)), iodine monobromide (IBr) and iodine (I(2)) with single-walled carbon nanotubes (SWNTs) and graphene has been investigated in detail. Halogen doping of the two nanocarbons has been examined using Raman spectroscopy in conjunction with electronic absorption spectroscopy and extensive theoretical calculations. The halogen molecules, being electron withdrawing in nature, induce distinct changes in the electronic states of both the SWNTs and graphene, which manifests with a change in the spectroscopic signatures. Stiffening of the Raman G-bands of the nanocarbons upon treatment with the different halogen molecules and the emergence of new bands in the electronic absorption spectra, both point to the fact that the halogen molecules are involved in molecular charge-transfer with the nanocarbons. The experimental findings have been explained through density functional theory (DFT) calculations, which suggest that the extent of charge-transfer depends on the electron affinities of the different halogens, which determines the overall spectroscopic properties. The magnitude of the molecular charge-transfer between the halogens and the nanocarbons generally varies in the order ICl > Br(2) > IBr > I(2), which is consistent with the expected order of electron affinities.

Implication of a sigma-Methane Complex en Route to Elimination of Methane from a Ruthenium Complex: An Experimental and Theoretical Investigation

The five-coordinated 16-electron complex Ru(Me)(dppe)(2)]OTf] (3) undergoes methane elimination at room temperature to afford the ortho-metalated species (dppe){(C6H5)(C6H4)PCH2CH2P(C6H5)(2)}Ru]OTf] (7). Methane elimination, monitored using NMR spectroscopy, revealed no intermediate throughout the reaction. The NOE between Ru-Me protons and ortho phenyl protons and an agostic interaction trans to the methyl group were found in complex 3 by NMR spectroscopy, which form the basis for three plausible pathways for methane elimination and ortho metalation: pathway I (through spatial interaction), pathway II (through oxidative addition and reductive elimination), and pathway III (through agostic interaction). Methane elimination from complex 3 via pathway I was discounted, since it involves interactions through space and not through bonds. Moreover, the calculated energy barrier for the pathway I transition state was quite high (71.3 kcal/mol), which also indicates that this pathway is very unlikely. Furthermore, no spectroscopic evidence for oxidatively added seven-coordinated Ru(IV) species was found and the computed energy barrier of the transition state for pathway II was moderately high (41.1 kcal/mol), which suggests that this cannot be the right pathway for methane elimination and ortho-metalation of complex 3. On the other hand, indirect evidence in the form of chemical reactions point to the most plausible pathway for methane elimination, pathway III, via the intermediacy of a sigma-CH4 complex that could not be found spectroscopically. DFT calculations at several levels on this pathway showed an initial low-barrier rearrangement through TS1 to a square-pyramidal intermediate wherein methyl and agostic C-H are cis to each other. Migration of hydrogen from agostic C-H and elimination of methane proceed through the transition state TS2, which retains a weak metal-H bonding through most parts of the reaction coordinate. Upon comparison of all three pathways, pathway III was found to be the most likely for methane elimination and ortho-metalation of complex 3.

Efectos de la utilización de la hoja de Nim (Azadirachta indica), en relación al levamisol como desparasitante interno en cabras nubias en el Centro de Experimentación y Capacitación Agropecuaria (CECA), Granada, Nicaragua

El presente estudio se realizó en el CECA (Centro de Experimentación y Capacitación Agropecuaria), ubicado al Noreste de la ciudad de Granada, siendo el clima catalogado como clima tropical de sabana con una biotemperatura de 17-24°C y humedad relativa de) 68-85%. El ensayo tuvo una duración de 37 días comprendidos entre los meses de Julio y Agosto de 1994. Con el objetivo de comprar el efecto de la utilización del té de hojas de Nim (Azadirachta indica) como desparasitante interno botánico realizando un análisis comparativo con el producto químico Levamisol en el control de endoparásitos en cabras reproductoras en edades de 2-5 años. Se les realizaron análisis coprológicos al inicio del ensayo para diagnosticar las especies parasitarias y la intensidad de las cargas parasitarias, para este análisis se les realizó en el laboratorio del MAG la prueba de flotación y sedimentación resultando por orden de importancia los géneros: Strongylata, Strongyloides, Coccidias, Paramphistomun, Trichostrongylus y Haemonchus. A continuación se procedió a la aplicación del té de hojas de Nim Azadirachta indica) por vía oral, formando dos grupos para el tratamiento botánico, uno tratado con 150 hojas y otro con 250 hojas y un tercero tratado con desparasitante interno químico Levamisol en dosis de 3 ce por UE vía intramuscular. Después de aplicar los tratamientos se procedió a tomar muestras de heces a los 7, 14,21 y 30 días post-tratamiento. Al realizar el análisis comparativo de los tratamientos respecto a las cargas parasitarias y especies parasitarias resultó que los niveles de efectividad se obtuvieron a los 14 días con los tratamientos botánicos Nim 250 y químico Levamisol. El porcentaje de efectividad con Nim 250 fue del 83.3% para la especie Strongyloides y el tratamiento Levamisol del l00%, mostrando para Coocidia una efectividad del 83.3% para Nim 250.

Utilización de la hoja de Neem (Azadirachta indica, A Juss) como desparasitante en terneros lactantes con edad de tres a cinco meses

El presente estudio se realizó en la finca "Toro Overo", ésta se encuentra ubicada en el municipio de Mateare departamento de Managua, el clima es ondeante con temperatura promedio de 26 a 32°C. La zona ecológica es de sabana tropical. La duración del experimento fue de 30 días a partir de la selección e identificación de los animales bajo los tratamientos evaluados. Con el objetivo de comparar el efecto del extracto acuoso de Neem en diferentes concentraciones versus Levamisol en el control de endoparásitos en terneros de 3 a 5 meses. Se seleccionaron 30 animales con edades promedio de 3 a 5 meses, estos se dividieron en 3 grupos, cada grupo formado por 10 animales por tratamiento, Tratamiento I: Levamisol (11.79%) a razón de 1 ce por 20 kg de peso vivo por vía intramuscular. Tratamiento II. Desparasitante interno botánico a base de un preparado de 250 hojas verdes de Neem, se le suministró la cantidad de 250 ce por cada animal vía oral. Tratamiento III: Desparasitante interno botánico a base de un preparado acuoso de 350 hojas verdes de Neem se le suministró la cantidad de 250 ce por cada animal vía oral. A los animales se les realizó análisis coprológico al inicio del ensayo para diagnosticar las especies parasitarias y la intensidad de las cargas parasitarias. Posteriormente se realizaron muestreos coprológicos a los 7, 14, 21 y 30 días post aplicación, para esto se utilizaron las pruebas de sedimentación y flotación identificando los géneros, mediante la cámara de Mac Master. Se identificaron tres géneros de parásitos, entre ellos se encontró al género Coccideas, Strongyloides y Dictyocau/us por orden de importancia y presentación. Para él genero Strongy/oides la efectividad de los tratamientos con Neem (250, 350) y Levamisol fue a los 7 días. Mientras que para el género Coccidea la mayor efectividad de los tres tratamientos se alcanzó a los 14 días. Y para el género Dictyocaulus ninguno de los tres tratamientos ejerció efecto. Desde el punto de vista económico con base en los costos se encontró factible el uso de los tratamientos botánicos.

Estudio preliminar de la utilizacion del aceite y resina de Neem (Azadirachta indica A. Juss) en el tratamiento de la sarna Psoroptica equina en la comarca Pilar del municipio de Santo Domingo, departamento de Chontales

El presente estudio se realizó en la finca "El Porvenir" ubicada en los 12°15' de latitud norte y 85"04' de longitud oeste, en el municipio de Santo Domingo departamento de Chontales, el clima es de sabana tropical con temperaturas entre 25 a 27"C. La duración del experimento fue de 18 días a partir de la selección e identificación de los animales bajo los tratamientos evaluados. Con el objetivo de comparar el efecto del aceite y resina de Neem al 40 % versus lvermectina pasta al 1% en el control de la sama Psoróptica equina. Se utilizó un Diseño Completamente al Azar (D.C.A.). Se seleccionaron 21 equinos con edades promedios de 1O a l 5 años, estos se dividieron en 3 grupos, cada grupo formado por 7 equinos por tratamiento, Tratamiento P: Ivermectina pasta 1% a razón de lg por cada 100 kg de peso vivo, vía oral. Tratamiento A:aceite de Neem acaricida tópico botánico a base de aceite de Neem, se aplicó vía tópica un promedio de 20 mi por cada animal. Tratamiento R: resina de Neem, acaricida tópico botánico a base de resina de Neem, se aplicó vía tópica, un promedio de 20 mi por cada equino. A los equinos se les realizó un examen clinico al inicio del ensayo y a los 14 días post aplicación, se utilizó el diagnóstico clínico y sintomatológico para evaluar el comportamiento de los tratamientos. Para cuantificar las reducciones de las lesiones se utilizaron tres variables: detención, reducción y control de las lesiones. Los tratamientos con Neem aceite y resina al 400/o arrojaron los siguientes resultados: Aceite 40% logró alcanzar un 100% del control de las lesiones y la resina alcanzó 86%. La Ivermectina pasta 1% sólo alcanzó la reducción de las lesiones en un 100%. Entre los tres tratamientos, el que dio mejores resultados fue el aceite de Neem al 40% con un porcentaje de eficiencia en el control de la sama equina en un 100%.

El lenguaje místico en Santa Catalina de Siena

Resumen: El lenguaje místico posee características propias, una de ellas es la inefabilidad. En este artículo la autora, basándose en los conceptos elaborados por M. De Certeau, analiza en primer lugar los rasgos que posee este lenguaje en la obra de Santa Catalina de Siena. En segundo lugar el artículo explora la matriz epistolar que posee Il Dialogo della Divina Provvidenza, la obra más importante de la santa. Aquí se observa de qué manera una gramática hablada conserva las entonaciones propias de la meditación que le da origen. Teniendo su origen en una carta Il Dialogo no sólo manifiesta el lenguaje oral usado en su época sino su estatuto privado y público a la vez.

Rendimiento y calidad de las interacciones sociocognitivas en díadas que trabajan colaborativamente en forma presencial y por chat

Resumen: En este trabajo se examina el rendimiento de estudiantes universitarios en razonamiento formal con y sin interacción social. La muestra N = 83 estuvo conformada por alumnos provenientes de dos universidades (UNMDP y UAA) quienes fueron asignados a dos condiciones: experimental con interacción (n = 40) y grupo control sin interacción (n = 43). El reactivo empleado consistió en una serie de pruebas del Test de Matrices Progresivas escala general y avanzada. Todos los participantes debieron resolver dichas tareas durante varias semanas: primero en forma individual (pretest), luego en forma colectiva presencial y por chat (díadas, condición experimental) y en forma individual (grupo control), y finalmente en forma individual (postest). Se registraron las interacciones que llevaron a cabo los participantes mediante videofilmación y logs del Chat. El rendimiento fue evaluado según la condición asignada: individual o grupal y en los últimos mediante una evaluación interjueces se estableció la calidad de las interacciones. Los resultados corroboran la superioridad de las díadas por sobre la performance individual; la reiteración en la fase de postest de aquellos ítems incorrectamente resueltos en el pretest más el agregado de nuevos ejercicios pusieron de relieve dos zonas de avance o de internalización de los progresos. En cuanto a la calidad de las interacciones, las mismas son coincidentes. Estos resultados abren nuevos interrogantes acerca del conflicto sociocognitivo y su papel para el avance grupal – individual.