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Terms modified by Meta Selected AbstractsHigh-performance separation of small inorganic anions on a methacrylate-based polymer monolith grafted with [2(methacryloyloxy)ethyl] trimethylammonium chlorideJOURNAL OF SEPARATION SCIENCE, JSS, Issue 15-16 2009Damian Connolly Abstract A glycidyl methacrylate- co -ethylene dimethacrylate monolith in capillary format (100 ,m/id) has been grafted with chains of poly([2(methacryloyloxy)ethyl] trimethylammonium chloride (poly-META) and applied to the ion-chromatographic separation of selected inorganic anions. Grafting chains of META onto the generic monolithic scaffold resulted in a monolith with ,electrolyte responsive flow permeability', which manifested as increased permeability in the presence of electrolyte solutions. Using an eluent of 2 mM sodium benzoate and on-column contactless conductivity detection, a test mixture of six common anions was isocratically separated and detected within 12 min, with the first four anions baseline resolved within a retention time window of 3.2 min. Retention time precision was ,1.2% for all anions tested. Separation efficiencies of 15 000 N/m were achieved for fluoride at 1 ,L/min, with column efficiencies up to 29 500 N/m obtained at a lower flow rate of 100 nL/min. Furthermore, repeatability of the column modification procedure using photografting methods was acceptable, with retention times between replicate columns matching within 9%. [source] Listening to God: Using Meta,Terminology to Describe Revelation in a Comparative Theistic Context1DIALOG, Issue 2 2009A. J. Watson Abstract:, Starting from the assertion that comparative theology is inherently dialogical in nature, this paper examines the use of non-confessional meta-terminology and its application in interfaith dialogue. In so doing, it examines potential meta-terms for describing revelation as related in the Bhagavad-Gita, the Qur'an, and the Gospel of John, and concludes that non-confessional terms aid in the dismissal of normative viewpoints, leading to greater appreciation of commonality and meaning in the truth claims of other faiths and dialogue partners. [source] Solvent-Induced Self-Assembly of a Meta -Linked Conjugated Polyelectrolyte.ADVANCED MATERIALS, Issue 14 2004Amplified Quenching, Guest Intercalation, Helix Formation A water-soluble meta -linked poly(phenylene ethynylene) is shown to fold into a helical conformation in water. The helix is stabilized by solvophobic forces and ,-stacking interactions. The metallo-intercalator complex Ru(dppz)(phen)22+ binds to the helical polymer via intercalation and the complex is highly luminescent when it is bound to the polymer (see Figure). [source] Can Basic Individual Differences Shed Light on the Construct Meaning of Assessment Center Evaluations?INTERNATIONAL JOURNAL OF SELECTION AND ASSESSMENT, Issue 1 2003J. M. Collins The construct meaning of assessment center evaluations is an important unresolved issue in I/O psychology. This study hypothesized that Cognitive Ability and personality traits are primary correlates of evaluators' overall assessment ratings (OARs). Meta,analysis results based on 65 correlations indicate the following mean construct,level correlations with OARs: .67 for Cognitive Ability, .50 for Extraversion, .35 for Emotional Stability, .25 for Openness, and .17 for Agreeableness; yielding a multiple R of .84. These findings support our hypothesis and cast light on the construct meaning of assessment center evaluations. [source] Micromorphology of resin,dentin interfaces using one-bottle etch&rinse and self-etching adhesive systems on laser-treated dentin surfaces: A confocal laser scanning microscope analysisLASERS IN SURGERY AND MEDICINE, Issue 7 2010Marcelo Tavares de Oliveira DDS Abstract Background and Objectives This study evaluated the hybrid layer (HL) morphology created by three adhesive systems (AS) on dentin surfaces treated with Er:YAG laser using two irradiation parameters. Study Design Occlusal flat dentin surfaces of 36 human third molars were assigned into nine groups (n,=,4) according to the following ASs: one bottle etch&rinse Single Bond Plus (3M ESPE), two-step Clearfil Protect Bond (Kuraray), and all-in-one S3 Bond (Kuraray) self-etching, which were labeled with rhodamine B or fluorescein isothiocyanate,dextran and were applied to dentin surfaces that were irradiated with Er:YAG laser at either 120 (38.7,J/cm2) or 200,mJ/pulse (64.5,J/cm2), or were applied to untreated dentin surfaces (control group). The ASs were light-activated following MI and the bonded surfaces were restored with resin composite Z250 (3M ESPE). After 24,hours of storage in vegetable oil, the restored teeth were vertically, serially sectioned into 1-mm thick slabs, which had the adhesive interfaces analyzed with confocal laser microscope (CLSM,LSM 510 Meta). CLSM images were recorded in the fluorescent mode from three different regions along each bonded interface. Results Non-uniform HL was created on laser-irradiated dentin surfaces regardless of laser irradiation protocol for all AS, while regular and uniform HL was observed in the control groups. "Stretch mark"-like red lines were found within the HL as a result of resin infiltration into dentin microfissures, which were predominantly observed in 200,mJ/pulse groups regardless of AS. Poor resin infiltration into peritubular dentin was observed in most regions of adhesive interfaces created by all ASs on laser-irradiated dentin, resulting in thin resin tags with neither funnel-shaped morphology nor lateral resin projections. Conclusion Laser irradiation of dentin surfaces at 120 or 200,mJ/pulse resulted in morphological changes in HL and resin tags for all ASs evaluated in the study. Lasers Surg. Med. 42:662,670, 2010. © 2010 Wiley-Liss, Inc. [source] The Self,Concept of Students with Learning Disabilities: A Meta,Analysis of Comparisons Across Different PlacementsLEARNING DISABILITIES RESEARCH & PRACTICE, Issue 4 2002Batya ElbaumArticle first published online: 17 DEC 200 Although placement in less restrictive settings is generally believed to be associated with more positive social outcomes for students with disabilities, the empirical research has yielded equivocal findings. The purpose of this study was to synthesize the empirical research comparing the self,concept of students with learning disabilities (LD) in different educational placements. Meta,analysis revealed no overall association between self,concept and educational placement for four out of five comparisons: regular class vs. resource room, regular class vs. self,contained class, resource room vs. self,contained class, and regular class vs. special school. Students with LD receiving instruction in self,contained classrooms in regular schools exhibited lower self,concept compared to students with LD attending special schools. Follow,up analyses were conducted to explore whether the variability of effect sizes in regular class,resource room comparisons was associated with any of several potential moderator variables; the only variable for which the association approached significance was whether students in the regular classroom were provided with appropriate special education supports and services. The findings are discussed in light of documented individual variation in students' placement preferences. [source] Alpha-retinals as Rhodopsin Chromophores,Preference for the 9- Z Configuration and Partial Agonist Activity,PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 4 2008Yajie Wang The visual pigment rhodopsin, the photosensory element of the rod photoreceptor cell in the vertebrate retina, shows in combination with an endogenous ligand, 11- Z retinal, an astonishing photochemical performance. It exhibits an unprecedented quantum yield (0.67) in a highly defined and ultrafast photoisomerization process. This triggers the conformational changes leading to the active state Meta(rhodopsin) II. Retinal is covalently bound to Lys-296 of the protein opsin in a protonated Schiff base. The resulting positive charge delocalization over the terminal part of the polyene chain of retinal creates a conjugation defect that upon photoexcitation moves to the opposite end of the polyene. Shortening the polyene as in 4,5-dehydro,5,6-dihydro (alpha), 5,6-dihydro or 7,8-dihydro-analogs might facilitate photoisomerization of a 9- Z and a 11- Z bond. Here we describe pigment analogs generated with bovine opsin and 11- Z or 9- Z 4,5-dehydro,5,6-dihydro-retinal that were further characterized by UV,Vis and FTIR spectroscopy. The preference of opsin for native 11- Z retinal over the 9- Z isomer is reversed in 4,5-dehydro,5,6-dihydro-retinal. 9- Z 4,5-dehydro,5,6-dihydro-retinal readily generated a photosensitive pigment. This modification has no effect on the quantum yield, but affects the Batho,blueshifted intermediate (BSI) equilibrium and leads to a strong decrease in the G-protein activation rate because of a downshift of the pKa of the Meta I,Meta II equilibrium. [source] Meta -selektive übergangsmetallkatalysierte C-H-Bindungsfunktionalisierung in Arenen,ANGEWANDTE CHEMIE, Issue 39 2009Yang Zhou Meta(i)lle für Position drei! Fortschritte bei übergangsmetallkatalysierten meta -selektiven Funktionalisierungen von aromatischen C-H-Bindungen werden vorgestellt (siehe Schema; EDG, EWG: elektronenschiebende bzw. elektronenziehende Gruppe). Die Methoden ergänzen die bisher bekannten Verfahren und könnten der Synthese vormals schwer zugänglicher Produkte zahlreiche Möglichkeiten eröffnen. Mögliche Reaktionsmechanismen werden diskutiert. [source] Ototoxicity in Rats Exposed to Ortho-, Meta- and Para-Xylene Vapours for 13 WeeksBASIC AND CLINICAL PHARMACOLOGY & TOXICOLOGY, Issue 1 2001François Gagnaire Brainstem auditory-evoked responses were used to determine auditory thresholds at different frequencies. Among the three isomers studied, only para-xylene produced moderate to severe ototoxicity in rats exposed at 900 and 1800 p.p.m. Increased auditory thresholds were observed at 2, 4, 8 and 16 kHz in rats exposed to 1800 p.p.m. para-xylene. The auditory threshold shifts (35 to 38 dB) did not reverse after 8 weeks of recovery. Moderate and severe losses of outer hair cells of the organ of Corti occurred in animals exposed to 900 and 1800 p.p.m. para-xylene respectively. Thus, the no observed effect level of para-xylene was 450 p.p.m. based on the loss of outer hair cells observed by light and electron microscopy. [source] Susceptibility of Common and Rare Plant Species to the Genetic Consequences of Habitat FragmentationCONSERVATION BIOLOGY, Issue 3 2007OLIVIER HONNAY diversidad genética; endogamia; fragmentación de hábitat; sistema reproductivo; tamaño poblacional Abstract:,Small plant populations are more prone to extinction due to the loss of genetic variation through random genetic drift, increased selfing, and mating among related individuals. To date, most researchers dealing with genetic erosion in fragmented plant populations have focused on threatened or rare species. We raise the question whether common plant species are as susceptible to habitat fragmentation as rare species. We conducted a formal meta-analysis of habitat fragmentation studies that reported both population size and population genetic diversity. We estimated the overall weighted mean and variance of the correlation coefficients among four different measures of genetic diversity and plant population size. We then tested whether rarity, mating system, and plant longevity are potential moderators of the relationship between population size and genetic diversity. Mean gene diversity, percent polymorphic loci, and allelic richness across studies were positively and highly significantly correlated with population size, whereas no significant relationship was found between population size and the inbreeding coefficient. Genetic diversity of self-compatible species was less affected by decreasing population size than that of obligate outcrossing and self-compatible but mainly outcrossing species. Longevity did not affect the population genetic response to fragmentation. Our most important finding, however, was that common species were as, or more, susceptible to the population genetic consequences of habitat fragmentation than rare species, even when historically or naturally rare species were excluded from the analysis. These results are dramatic in that many more plant species than previously assumed may be vulnerable to genetic erosion and loss of genetic diversity as a result of ongoing fragmentation processes. This implies that many fragmented habitats have become unable to support plant populations that are large enough to maintain a mutation-drift balance and that occupied habitat fragments have become too isolated to allow sufficient gene flow to enable replenishment of lost alleles. Resumen:,Las poblaciones pequeñas de plantas son más propensas a la extinción debido a la pérdida de variación genética por medio de la deriva génica aleatoria, el incremento de autogamia y la reproducción entre individuos emparentados. A la fecha, la mayoría de los investigadores que trabajan con erosión genética en poblaciones fragmentadas de plantas se han enfocado en las especies amenazadas o raras. Cuestionamos si las especies de plantas comunes son tan susceptibles a la fragmentación del hábitat como las especies raras. Realizamos un meta análisis formal de estudios de fragmentación que reportaron tanto tamaño poblacional como diversidad genética. Estimamos la media general ponderada y la varianza de los coeficientes de correlación entre cuatro medidas de diversidad genética y de tamaño poblacional de las plantas. Posteriormente probamos si la rareza, el sistema reproductivo y la longevidad de la planta son moderadores potenciales de la relación entre el tamaño poblacional y la diversidad genética. La diversidad genética promedio, el porcentaje de loci polimórficos y la riqueza alélica en los estudios tuvieron una correlación positiva y altamente significativa con el tamaño poblacional, mientras que no encontramos relación significativa entre el tamaño poblacional y el coeficiente de endogamia. La diversidad genética de especies auto compatibles fue menos afectada por la reducción en el tamaño poblacional que la de especies exogámicas obligadas y especies auto compatibles, pero principalmente exogámicas. La longevidad no afectó la respuesta genética de la población a la fragmentación. Sin embargo, nuestro hallazgo más importante fue que las especies comunes fueron tan, o más, susceptibles a las consecuencias genéticas de la fragmentación del hábitat que las especies raras, aun cuando las especies histórica o naturalmente raras fueron excluidas del análisis. Estos resultados son dramáticos porque muchas especies más pueden ser vulnerables a la erosión genética y a la pérdida de diversidad genética como consecuencia de los procesos de fragmentación que lo se asumía previamente. Esto implica que muchos hábitats fragmentados han perdido la capacidad para soportar poblaciones de plantas lo suficientemente grandes para mantener un equilibrio mutación-deriva y que los fragmentos de hábitat ocupados están tan aislados que el flujo génico es insuficiente para permitir la reposición de alelos perdidos. [source] Nonindigenous Species: Ecological Explanation, Environmental Ethics, and Public PolicyCONSERVATION BIOLOGY, Issue 1 2003David M. Lodge Misunderstandings and tension exist regarding the science, values, environmental ethics, and public policy relevant to invasive species, which are the subset of nonindigenous species that cause economic or environmental damage. Although there is a natural background rate at which species invasions occur, it is much lower than the current human-induced rates at which species are being moved around the globe. Contrary to some recently voiced opinions , the fact that some species invasions occur without human assistance does not confer acceptability on all species invasions. Also, despite claims to the contrary, the reductions of native biodiversity caused by nonindigenous species are large and well documented. Even if that were not true, an emphasis on species numbers alone as a metric for the impact of nonindigenous species does not adequately incorporate the high value many humans place on the uniqueness of regional biota. Because regional biota are being homogenized by species invasions, it has become an appropriate and official public policy goal in the United States to reduce the harm done by invasive species. The goal is not, however, a reduction of numbers of nonindigenous species per se, as recently claimed by some authors, but a reduction in the damage caused by invasive species, including many sorts of environmental and economic damage. A major challenge remaining for ecology, environmental ethics, and public policy is therefore the development of widely applicable risk-assessment protocols that are acceptable to diverse constituencies. Despite apparent disagreements among scholars, little real disagreement exists about the occurrence, effects, or public-policy implications of nonindigenous species. Resumen: El público está recibiendo un mensaje confuso de ecologistas, otros académicos y periodistas sobre el tema de especies no nativas. Existen malos entendidos y tensión en relación con la ciencia, los valores, la ética ambiental y las políticas públicas relevantes a las especies invasoras, que son un subconjunto de las especies no nativas que causan daños económicos o ambientales. Aunque existe una tasa natural a la que ocurren invasiones, es mucho más baja que las actuales tasas, inducidas por humanos, a las que especies son movidas alrededor del mundo. Al contrario de algunos autores recientes, el hecho de que algunas invasiones de especies ocurren sin asistencia humana no le confiere aceptabilidad moral sobre todas las invasiones de especies. También, a pesar de recientes afirmaciones de lo contrario, las reducciones de biodiversidad nativa debido a especies no nativas son notables y están bien documentadas. Aún si no fuera verdad, el énfasis sólo en el número de especies como una medida del impacto de especies no nativas no incorpora adecuadamente el alto valor que muchos humanos reconocen en la singularidad de la biota regional. Debido a que la biota regional está siendo homogeneizada por invasiones de especies, la reducción del daño causado por especies invasoras se ha convertido en una política pública apropiada y oficial en los Estados Unidos. Sin embargo, la meta no es la reducción de especies no nativas, en si, como afirman algunos autores recientes, sino una reducción de los impactos dañinos de las especies invasoras, incluyendo muchos tipos de daño económico y ambiental. Por lo tanto, un reto mayor para la ecología, la ética ambiental y la política pública es el desarrollo de protocolos de evaluación de riesgos ampliamente aplicables que sean aceptables para electores diversos. A pesar de aparentes desacuerdos entre académicos, existe poco desacuerdo real acerca de la ocurrencia, el impacto o las implicancias en política pública de las especies no nativas. [source] Compositional effects on electrophoretic and chromatographic figures of merit in electrokinetic chromatography with cetyltrimethylammonium bromide/sodium octyl sulfate vesicles as the pseudostationary phase.ELECTROPHORESIS, Issue 5 2008Part 1: Effect of the phase ratio Abstract The effect of the phase ratio on the electrophoretic and chromatographic properties of unilamellar vesicles comprised of cetyltrimethylammonium bromide (CTAB) and sodium octyl sulfate (SOS) was investigated in EKC. The surfactant concentration of the vesicles was 0.9, 1.2, 1.5, and 1.8% w/v, with a mole ratio of 1:3.66 (CTAB/SOS). Results were compared to those obtained using SDS micelles at concentrations of 1.0% (w/v, 35,mM) and 1.5% (52,mM). The CTAB/SOS vesicles (0.9,1.8% w/v) provided a significantly larger elution range (5.7,,,tves/t0,,,8.7) and greater hydrophobic (methylene) selectivity (2.8,,,,CH2,,,3.1) than SDS micelles (3.1,,,tmc/t0,,,3.3; ,CH2,=,2.2). Whereas the larger elution range can be attributed to the 25% reduction in EOF due to the interaction of unaggregated CTAB cations and the negatively charged capillary wall, the higher methylene selectivity is likely due to the lower concentration of water expected in the CTAB/SOS vesicle bilayer compared to the Palisades layer of SDS micelles. For a given phase ratio, CTAB/SOS vesicles are somewhat less retentive than SDS micelles, although retention factors comparable to those observed in 1.0,1.5% SDS can be obtained with 1.5,1.8% CTAB/SOS. A linear relationship was observed between phase ratio and retention factor, confirming the validity of the phase ratio model for these vesicles. Unique polar group selectivities and positional isomer shape selectivities were obtained with CTAB/SOS vesicles, with both types of selectivities being nearly independent of the phase ratio. For four sets of positional isomers, the elution order was always para < ortho < meta. Finally, the thermodynamics of solute retention was qualitatively similar to that reported for other surfactant aggregates (micelles and microemulsions); the enthalpic contribution to retention was consistently favorable for all compounds, whereas the entropic contribution was favorable only to hydrophobic solutes. [source] Persistent or not persistent?ENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 10 2009Polychlorinated biphenyls are readily depurated by grizzly bears (Ursus arctos horribilis) Abstract Major pharmacokinetic processes influencing polychlorinated biphenyl (PCB) accumulation in mammals include uptake, biotransformation, respiration, and excretion. We characterized some of the factors underlying PCB accumulation/loss by evaluating PCB concentrations and patterns in pre- and posthibernation grizzly bears (Ursus arctos horribilis) and their prey. The PCB congeners with vicinal meta - and para -chlorine unsubstituted hydrogen positions consistently showed loss both before and during hibernation, supporting the idea of a dominant role for biotransformation. Retention of all other studied congeners relative to that of PCB 194 varied widely (from <1 to 100%) and was highly correlated with log octanol--water partition coefficient (p < 0.0001). A lack of loss for most of these other congeners during hibernation supports the notion that excretion (e.g., fecal or urinary) or lack of uptake during the feeding season underlies their lack of accumulation, because hibernating bears do not eat or excrete. We estimate that grizzly bears retain less than 10% of total PCBs taken up from their diet. Our results suggest that for grizzly bears, depuration of PCBs via biotransformation is important (explaining ,40% of loss), but that nonbiotransformation processes, such as excretion, may be more important (explaining ,60% of loss). These findings, together with the approximately 91% loss of the persistent PCB 153 congener relative to PCB 194 in grizzly bears, raise important questions about how one defines persistence of PCBs in wildlife and may have bearing on the interpretation of food-web biomagnification studies. [source] Hepatic microsomal cytochrome P450 enzyme activity in relation to in vitro metabolism/inhibition of polychlorinated biphenyls and testosterone in Baltic grey seal (Halichoerus grypus)ENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 3 2003Hongxia Li Abstract Among other factors, cytochrome P450 (CYP) enzyme activity determines polychlorinated biphenyl (PCB) bioaccu-mulation, biotransformation, and toxicity in exposed species. We measured the oxidative metabolism in vitro of 12 PCB congeners, representing structural groups based on the number and position of the chlorine atoms, by the hepatic microsomes of one Baltic grey seal (Halichoerus grypus). Microsomal metabolism was observed for several PCBs with vicinal H atoms exclusively in the ortho and meta positions and without any ortho -Cl substituents (CB-15 [4,4,-Cl2] and CB-77 [3,3,,4,4,-Cl4]), vicinal meta and para -H atoms (CB-52 [2,2,,5,5,-Cl4], and ,101 [2,2,,4,5,5,-Cl5]) or with both characteristics in combination with either only one ortho -Cl (CB-26 [2,3,,5-Cl3], CB-31 [2,4,,5-Cl3]) or two ortho -Cl substituents (CB-44 [2,2,,3,5,-Cl4]). To allocate PCB biotransformation to specific CYPs, the inhibitive effect of compounds with known CYP-specific inhibition properties was assessed on in vitro PCB metabolism and on regio- and stereospecific testosterone hydroxylase activities. Metabolic inhibition was considered relevant at concentrations ,1.0 ,M because these inhibitors became decreasingly selective at higher concentrations. At <1.0 ,M, ellipticine (CYP1A1/2 inhibitor) selectively inhibited CB-15, ,26, ,31, and ,77 metabolism, with no significant inhibition of CB-44, ,52, and ,101 metabolism. Inhibition of CB-52 and ,101 metabolism by chloramphenicol (CYP2B inhibitor) started at 1.0 ,M and maximized at about 100% at 10 ,M. Ketoconazole (CYP3A inhibitor) appeared to selectively inhibit CB-26, ,31, and ,44 metabolism relative to CB-15, ,77, and ,52 at concentrations ,1.0 ,M. Major testosterone metabolites formed in vitro were 2,-(CYP3A), 6,- (CYP3A, CYP1A), and 16,- (CYP2B) hydroxytestosterone and androstenedione (CYP2B, CYP2C11). The CYP forms indicated are associated with the specific metabolism of testosterone in laboratory animals. Inhibition of 2,- and 6,-hydroxytestosterone formation at ellipticine and ketoconazole concentrations ,1.0,M suggested that both inhibitors were good substrates of CYP3A-like enzymes in grey seal. Chloramphenicol (model for CYP2B) is apparently not a good inhibitor of CYP1A and CYP3A activities in grey seal because the chemical did not inhibit any metabolic route of testosterone at concentrations from 0.1 to 10 ,M. Our findings demonstrated that at least CYP1A- and CYP3A-like enzymes in the liver of grey seals are capable of metabolizing PCBs with ortho - meta and/or meta - para vicinal hydrogens. A CYP2B form might also be involved, but this could not be proven by the results of our experiments. Defining the profiles of CYP enzymes that are responsible for PCB biotransformation is necessary to fully understand the bioaccumulation, toxicokinetics, and risk of PCB exposure in seals and other free-ranging marine mammals. [source] meta -Terphenyl Phosphaalkenes Bearing Electron-Donating and -Accepting GroupsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 6 2010Vittal B. Gudimetla Abstract A set of para -substituted meta -terphenyl phosphaalkenes of the form 4-X-2,6-Mes2C6H2P=C(H)C6H4 -4-X, (X = H, MeO or NMe2; X, = H, CN, or NO2) have been synthesized to allow systematic studies of the impact of remote X and X, substituents on the phosphaalkene unit. The new compounds were characterized by 1H and 31P NMR spectroscopy, UV/Vis absorption spectroscopy, single X-ray crystal structures (for four compounds) and by electrochemical studies. The introduction of remote groups (X,) on the less hindered phenyl ring generated more significant effects on the physical properties of the materials than did substituents (X) on the hindered meta -terphenyl rings. These effects were also explored by computational methods in order to assess the influence of substituents on structures and properties. The polarization of these molecules is less than that produced for analogous alkenes, as the phosphaalkenes bear sterically demanding groups that constrain the systems to adopt conformations that are less than ideal for maximum ,-conjugation of the central , network [source] Solid-State Anion,Guest Encapsulation by Metallosupramolecular Capsules Made from Two Tetranuclear Copper(II) ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 29 2007Emilio Pardo Abstract A new cationic tetranuclear copper(II) complex self-assembles from one 1,3-phenylenebis(oxamato) (mpba) bridging ligand and four CuII ions partially blocked with N,N,N,,N, -tetramethylethylenediamine (tmen) terminal ligands. In the solid state, two of these tetracopper(II) oxamato complexes of bowl-like shape and helical conformation then serve as a building block for the generation of either hetero- (MP) or homochiral (MM/PP) dimeric capsules depending on the nature of the encapsulated anion guest, perchlorate or hexafluorophosphate. The overall magnetic behaviour of these metallosupramolecular capsules does not depend on the nature of the encapsulated anion guest, but it is consistent with the dimer-of-dimer structure of the tetracopper(II) cation host, where the interdimer magnetic coupling through the meta -phenylenediamidate bridge is negligibly smallrelative to the reasonably strong intradimer one across the oxamato bridge.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Benzene-di- N -substituted carbamates as conformationally constrained analogs of Pseudomonas lipase substratesEUROPEAN JOURNAL OF LIPID SCIENCE AND TECHNOLOGY, Issue 11 2007Ming-Cheng Lin Abstract Benzene-1,2-, -1,3-, and -1,4-di- N -substituted carbamates (1,15) are synthesized as the constrained analogs of gauche, eclipsed, and anti conformations of diesters of ethylene glycol, respectively. Carbamates 1,15 are characterized as the pseudo-substrate inhibitors of Pseudomonas species lipase. Long-chain carbamates are more potent inhibitors than short-chain ones. Different geometries of benzene-di-substituted carbamates, such as benzene-1,2-di- N -octylcarbamate (3) (ortho compound), benzene-1,3-di- N -octylcarbamate (8) (meta compound), and benzene-1,4-di- N -octylcarbamate (13) (para compound), show similar inhibitory potencies for the enzyme. In other words, kinetic data suggest that the enzyme does not discriminate ortho, meta, and para geometries of these constrained analogs. [source] Bis-Carbaborane-Bridged Bis-Glycophosphonates as Boron-Rich Delivery Agents for BNCTEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 16 2010Sven Stadlbauer Abstract The synthesis and properties of boron-rich bis(meta -carbaborane) derivatives containing glycophosphonate and glycophosphonothioate moieties are reported. All compounds are water-soluble; however, the tetragalactosylated compounds show lower solubility than their disodium salts. [source] An Efficient Synthesis of Substituted meta -Halophenols and Their Methyl Ethers: Insight into the Reaction MechanismEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 15 2010Faiz Ahmed Khan Abstract An expeditious synthetic methodology leading to substituted meta -halophenols and their corresponding methyl ether derivatives through acid-mediated fragmentation of suitably substituted dihalonorbornyl ketones has been devised. The reaction sequence consists of TBTH-mediated (TBTH is tri- n -butyltin hydride) selective bridgehead halogen reduction of easily accessible Diels,Alder adducts derived from 1,2,3,4-tetrahalo-5,5-dimethoxycyclopentadiene and ,-substituted vinyl acetates, with subsequent conversion into the requisite bicyclic ketones by a two-step hydrolysis/oxidation approach. An extensive mechanistic investigation based on isotope labeling and cross experiments has been carried out and plausible mechanistic pathways based on these results have been proposed. The absence of halogen atoms at the bridgehead positions steers the reaction through a novel pathway involving the incorporation of proton (or deuterium) followed by elimination of HX (or DX), so the described methodology also provides a reliable route to ortho-para dideuteratedphenolic derivatives. [source] Unexpected Tethering in the Synthesis of Methyl-Substituted Acetyl-1-oxaspiro[4.5]decanes: Novel Woody,Ambery Odorants with Improved Bioavailability,EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 2 2008Philip Kraft Abstract To study the olfactory properties of spirocyclic analogs of Iso Gamma (3) with improved water solubility and bioavailability, it was envisaged to spiroannulate 1-acetyl-1,2-dimethylcyclohexanone at the 4-position with a 3,3-dimethyltetrahydrofuran-2-yl moiety that would mimic the polarity of the double bond by its ether function. 3,3-Dimethyl-4-methylenehex-5-en-1-ol (9) was prepared by copper(I)-mediated 1,4-conjugate addition of the Grignard reagent of chloroprene (7) to 3-methylbut-2-enal with subsequent LAH reduction. However, the Diels,Alder reaction of diene 9 with (E)-3-methylpent-3-en-2-one in the presence of Me2AlCl unexpectedly provided exclusively the undesired meta adduct 10, as was discovered after cyclization to 11 with MeSO3H. The wrong selectivity was due to a tethering effect of the Lewis acid, and this could be evaded by changing the carbonyl function of the dienophile to a hydroxy group. Thereby the (5,R*,7,S*,8,S*)-configured 1-(4,,4,,7,,8,-tetramethyl-1,-oxaspiro[4.5]decan-7,/8,-yl)ethan-1-ones 11 and 14, as well as the like -configured 1-(4,,4,,7,-trimethyl-1,-oxaspiro[4.5]decan-7,/8,-yl)ethan-1-ones 16 and 19, were prepared selectively and studied for their odor characters, threshold values, and octanol/water partition coefficients. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Sequence-Selective Peptide Recognition with Designed ModulesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 1 2006Mark Wehner Abstract A concept for the rational design of sequence-selective peptide receptors has been extended: in addition to recognition modules for polar, aromatic and basic amino acids, the series has now been completed with new receptor units for apolar and acidic amino acids. The underlying strategy uses the intermolecular ,-sheet stabilization of a dipeptide as a prerequisite to bind its N-terminal amino acid side chain through a strategically placed recognition tip at the end of a U-turn protruding from the receptor moiety. Thus, a diaminopyrazole has been covalently attached to Kemp's triacid by way of a cyclic imide, while a meta -substituted aniline was coupled as an amide to the pendant third carboxylate arm, bringing the two aromatic units into a sub-van der Waals distance in a tight conformational lock. NMR titrations, Karplus analyses and Monte-Carlo simulations demonstrate the effective sequence-selective recognition of alanine-containing dipeptides. No example of such a rationally designed set of peptide receptors had existed previously. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Synthesis of Dihalo-Substituted Analogues of Tröger's Base from ortho - and meta -Substituted AnilinesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 16 2003Anna Hansson Abstract For the first time, ortho - and meta -halo-substituted anilines were successfully condensed with formaldehyde to dihalo-substituted analogues of Tröger's base. By using paraformaldehyde and TFA, yields of 2,85% of these potential supramolecular building blocks were obtained. Even the inconceivable achievement of condensing anilines unsubstituted in para -position to analogues of Tröger's base was successful. Adding our present results to our previous, makes it now possible to synthesize analogues of Tröger's base halo-substituted in almost any desired position in each of its two aromatic rings. In addition the first X-ray structure of a dihalo-substituted analogue of Tröger's base, 3,9-dibromo-4,10-dimethyl-6H,12H -5,11-methanodibenzo[b,f][1,5]diazocine (17), is presented. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Multifunctional Triphenylamine/Oxadiazole Hybrid as Host and Exciton-Blocking Material: High Efficiency Green Phosphorescent OLEDs Using Easily Available and Common MaterialsADVANCED FUNCTIONAL MATERIALS, Issue 17 2010Youtian Tao Abstract A new triphenylamine/oxadiazole hybrid, namely m -TPA- o -OXD, formed by connecting the meta -position of a phenyl ring in triphenylamine with the ortho -position of 2,5-biphenyl-1,3,4-oxadiazole, is designed and synthesized. The new bipolar compound is applicable in the phosphorescent organic light-emitting diodes (PHOLEDs) as both host and exciton-blocking material. By using the new material and the optimization of the device structures, very high efficiency green and yellow electrophosphorescence are achieved. For example, by introducing 1,3,5-tris(N -phenylbenzimidazol-2-yl)benzene (TPBI) to replace 2, 9-dimethyl-4,7-diphenyl-1, 10-phenanthroline (BCP)/tris(8-hydroxyquinoline)aluminium (Alq3) as hole blocking/electron transporting layer, followed by tuning the thicknesses of hole-transport 1, 4-bis[(1-naphthylphenyl)amino]biphenyl (NPB) layer to manipulate the charge balance, a maximum external quantum efficiency (,EQE,max) of 23.0% and a maximum power efficiency (,p,max) of 94.3 lm W,1 are attained for (ppy)2Ir(acac) based green electrophosphorescence. Subsequently, by inserting a thin layer of m -TPA- o -OXD as self triplet exciton block layer between hole-transport and emissive layer to confine triplet excitons, a ,EQE,max of 23.7% and ,p,max of 105 lm W,1 are achieved. This is the highest efficiency ever reported for (ppy)2Ir(acac) based green PHOLEDs. Furthermore, the new host m -TPA- o -OXD is also applicable for other phosphorescent emitters, such as green-emissive Ir(ppy)3 and yellow-emissive (fbi)2Ir(acac). A yellow electrophosphorescent device with ,EQE,max of 20.6%, ,c,max of 62.1 cd A,1, and ,p,max of 61.7 lm W,1, is fabricated. To the author's knowledge, this is also the highest efficiency ever reported for yellow PHOLEDs. [source] A novel coupled enzyme assay reveals an enzyme responsible for the deamination of a chemically unstable intermediate in the metabolic pathway of 4-amino-3-hydroxybenzoic acid in Bordetella sp. strain 10dFEBS JOURNAL, Issue 15 2004Chika Orii 2-Amino-5-carboxymuconic 6-semialdehyde is an unstable intermediate in the meta -cleavage pathway of 4-amino-3-hydroxybenzoic acid in Bordetella sp. strain 10d. In vitro, this compound is nonenzymatically converted to 2,5-pyridinedicarboxylic acid. Crude extracts of strain 10d grown on 4-amino-3-hydroxybenzoic acid converted 2-amino-5-carboxymuconic 6-semialdehyde formed from 4-amino-3-hydroxybenzoic acid by the first enzyme in the pathway, 4-amino-3-hydroxybenzoate 2,3-dioxygenase, to a yellow compound (,max = 375 nm). The enzyme in the crude extract carrying out the next step was purified to homogeneity. The yellow compound formed from 4-amino-3-hydroxybenzoic acid by this purified enzyme and purified 4-amino-3-hydroxybenzoate 2,3-dioxygenase in a coupled assay was identified as 2-hydroxymuconic 6-semialdehyde by GC-MS analysis. A mechanism for the formation of 2-hydroxymuconic 6-semialdehyde via enzymatic deamination and nonenzymatic decarboxylation is proposed based on results of spectrophotometric analyses. The purified enzyme, designated 2-amino-5-carboxymuconic 6-semialdehyde deaminase, is a new type of deaminase that differs from the 2-aminomuconate deaminases reported previously in that it primarily and specifically attacks 2-amino-5-carboxymuconic 6-semialdehyde. The deamination step in the proposed pathway differs from that in the pathways for 2-aminophenol and its derivatives. [source] Structures of the Reactive Intermediates in Organocatalysis with Diarylprolinol EthersHELVETICA CHIMICA ACTA, Issue 7 2009Abstract Structures of the reactive intermediates (enamines and iminium ions) of organocatalysis with diarylprolinol derivatives have been determined. To this end, diarylprolinol methyl and silyl ethers, 1, and aldehydes, PhCH2CHO, tBuCH2CHO, PhCH=CHCHO, are condensed to the corresponding enamines, A and 3 (Scheme,2), and cinnamoylidene iminium salts, B and 4 (Scheme,3). These are isolated and fully characterized by melting/decomposition points, [,]D, elemental analysis, IR and NMR spectroscopy, and high-resolution mass spectrometry (HR-MS). Salts with BF4, PF6, SbF6, and the weakly coordinating Al[OC(CF3)3]4 anion were prepared. X-Ray crystal structures of an enamine and of six iminium salts have been obtained and are described herein (Figs.,2 and 4,8, and Tables,2 and 7) and in a previous preliminary communication (Helv. Chim. Acta2008, 91, 1999). According to the NMR spectra (in CDCl3, (D6)DMSO, (D6)acetone, or CD3OD; Table,1), the major isomers 4 of the iminium salts have (E)-configuration of the exocyclic NC(1,) bond, but there are up to 11% of the (Z)-isomer present in these solutions (Fig.,1). In all crystal structures, the iminium ions have (E)-configuration, and the conformation around the exocyclic N-CC-O bond is synclinal-exo (cf.C and L), with one of the phenyl groups over the pyrrolidine ring, and the RO group over the , -system. One of the meta -substituents (Me in 4b, CF3 in 4c and 4e) on a 3,5-disubstituted phenyl group is also located in the space above the , -system. DFT Calculations at various levels of theory (Tables,3,6) confirm that the experimentally determined structures (cf. Fig.,10) are by far (up to 8.3,kcal/mol) the most stable ones. Implications of the results with respect to the mechanism of organocatalysis by diarylprolinol derivatives are discussed. [source] Photoswitches: From Molecules to MaterialsADVANCED MATERIALS, Issue 31 2010Maria-Melanie Russew Abstract Small organic molecules, capable of undergoing efficient and reversible photochemical reactions to switch them between (at least) two (meta)stable isomers associated with markedly different properties, continue to impact the materials world. Such photoswitches are being implemented in a variety of materials for applications ranging from optical devices to "smart" polymers. All approaches exploit the photoswitching molecular entities as gates, which translate an incoming light stimulus to trigger macroscopic property changes of the materials. In this progress report, the most promising recent examples in this field are highlighted and put in perspective. Moving from supramolecular systems in solution to surfaces and finally to bulk materials, important design concepts are discussed, emphasizing both the challenges as well as the great promise of such truly advanced materials. [source] The Role of Friends' Appearance and Behavior on Evaluations of Individuals on Facebook: Are We Known by the Company We Keep?HUMAN COMMUNICATION RESEARCH, Issue 1 2008Joseph B. Walther This research explores how cues deposited by social partners onto one's online networking profile affect observers' impressions of the profile owner. An experiment tested the relationships between both (a) what one's associates say about a person on a social network site via "wall postings," where friends leave public messages, and (b) the physical attractiveness of one's associates reflected in the photos that accompany their wall postings on the attractiveness and credibility observers attribute to the target profile owner. Results indicated that profile owners' friends' attractiveness affected their own in an assimilative pattern. Favorable or unfavorable statements about the targets interacted with target gender: Negatively valenced messages about certain moral behaviors increased male profile owners' perceived physical attractiveness, although they caused females to be viewed as less attractive. Résumé Le rôle de l'apparence et du comportement des amis dans l'évaluation d,individus sur Facebook : Notre entourage nous connaît-il? Cette recherche explore la façon dont des indices déposés par des partenaires sociaux sur le profil de réseautage en ligne d'une personne ont un effet sur les impressions qu,ont les observateurs du propriétaire de ce profil. Une expérience a testé la relation entre 1) ce que les amis d'une personne disent de celle-ci sur un site de réseautage social par le biais de messages publics laissés par ces amis sur son «Wall» (« mur » virtuel servant à afficher des messages) et 2) l,attrait physique des amis d'une personne telle que reflété par les photos qui accompagnent leurs messages publiés sur le «Wall», sur l,attrait et la crédibilité que des observateurs attribuent au propriétaire du profil ciblé. Les résultats indiquent que l'attrait des amis des propriétaires de profils a un impact sur le leur, selon un schéma d,assimilation. Des affirmations favorables ou défavorables aux cibles ont interagi avec le genre de la cible : des messages à valence négative à propos de certains comportements moraux ont augmenté l'attrait physique perçu des propriétaires de profils masculins, alors qu,ils faisaient en sorte que les propriétaires de sexe féminin étaient considérées moins attirantes. Abstract Die Rolle des Erscheinungsbildes und Verhaltens von Freunden bei der Evaluation von Personen bei Facebook: Was verraten die anderen über uns? Diese Studie untersucht, wie der Eindruck bezüglich des Profilinhabers durch Nachrichten, die auf Online-Networking-Profilen hinterlassen werden, beeinflusst wird. In einem Experiment untersuchten wir den Einfluss von 1) dem, was die Bekannten einer Person über diese via öffentlich lesbaren Pinnwandbotschaften sagen und 2) der physischen Attraktivität eines Freundes auf den beigefügten Fotos auf die Attraktivität und Glaubwürdigkeit, die Beobachter dem Profilbesitzer zuschreiben. Die Ergebnisse zeigen, dass die Attraktivität des Freundes die Attraktivität des Profilbesitzers auf vergleichbare Art und Weise beeinflusste. Positive oder negative Bemerkungen über das Zielprofil interagierten mit dem Geschlecht des Zielprofils. Negativ konnotierte Botschaften über das moralische Verhalten erhöhten bei männlichen Profilbesitzern die wahrgenommene physische Attraktivität, während sie bei weiblichen Profilbesitzern dazu führte, dass diese als weniger attraktiv wahrgenommen wurden. Resumen El Rol de la Apariencia y el Comportamiento de los Amigos sobre las Evaluaciones Individuales en Facebook: ¿Somos Conocidos por la Compañía que Mantenemos? Esta investigación explora cómo las claves depositadas por los compañeros sociales en el perfil de red online de uno mismo afectan las impresiones que los observadores tienen sobre el dueño de dicho perfil. Un experimento puso a prueba la relación entre (1) lo que sus asociados dicen acerca de una persona en la red social a través de los "mensajes de pared" donde los amigos dejan mensajes públicos, y (2) el atractivo físico de los asociados reflejado en las fotos que acompañan sus mensajes de pared, sobre el atractivo físico y la credibilidad que los observadores atribuyen al dueño del perfil. Los resultados indicaron que el atractivo físico de los amigos del dueño del perfil afectó el suyo propio en una pauta asimilativa. Las declaraciones favorables ó desfavorables sobre los perfiles metas interactuaron con el género meta: los mensajes de valencia negativa sobre ciertos comportamientos morales incrementaron la atracción física percibida del perfil masculino de los dueños, mientras que causó que las mujeres sean vistas como menos atractivas. ZhaiYao Yo yak [source] Preferential solvational effects on the Cr(VI) oxidation of benzylamines in benzene/2-methylpropan-2-ol mixturesINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 3 2010A. Thirumoorthi Imidazolium fluorochromate (IFC) oxidation of 11 meta- and para-substituted benzylamines, in varying mole fractions of benzene/2-methylpropan-2-ol binary mixtures, is first order in IFC and acid and zero order in substrate. The Hammett correlation yielded a U-shaped curve, indicating a change in the relative importance of bond formation and bond fission in the transition state. The rate data failed to correlate with macroscopic solvent parameters such as ,r and E. The correlation of kobs with Kamlet,Taft solvatochromic parameters suggests that H-bonding between the reacting species and the solvent plays a major role in governing the reactivity. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 159,167, 2010 [source] Studies on the kinetics of imidazolium fluorochromate oxidation of some meta - and para -substituted anilines in nonaqueous mediaINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 3 2006D. S. Bhuvaneshwari The imidazolium fluorochromate (IFC) oxidation of meta - and para -substituted anilines, in seven organic solvents, in the presence of p -toluenesulfonic acid (TsOH) is first order in IFC and TsOH and is zero order with respect to substrate. The IFC oxidation of 15 meta - and para -substituted anilines at 299,322 K complies with the isokinetic relationship but not to any of the linear free energy relationships; the isokinetic temperature lies within the experimental range. The specific rate of oxidizing species-anilines reaction (k2) correlates with substituent constants affording negative reaction constants. The rate data failed to correlate with macroscopic solvent parameters such as ,r and ENT. A correlation of rate data with Kamlet,Taft solvatochromic parameters (,, ,, ,*) suggests that the specific solute,solvent interactions play a major role in governing the reactivity, and the observed solvent effects have been explained on the basis of solute,solvent complexation. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 166,175, 2006 [source] Kinetics and mechanisms of transalkylation and disproportionation of meta -diethylbenzene by triflic acid catalystINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 11 2003S. M. Al-Zahrani The kinetics of transalkylation and isomerization of meta -diethylbenzene in the presence of benzene using triflic acid as a catalyst has been investigated. High catalytic activity of the triflic acid catalyst was observed in homogeneous liquid-phase reactions. On the basis of the product distribution obtained, transalkylation, disproportionation, and isomerization reactions have been considered and the main product of the reaction was ethylbenzene. These reactions are conducted in a closed liquid batch reactor with continuous stirring under dry nitrogen and atmospheric pressure over the temperature range of 288,308 K. The main transalkylation, disproportionation, and isomerization reactions occurred simultaneously and were considered as elementary reactions. The apparent activation energy of the transalkylation reaction was found to be 35.5 kJ/mol, while that of disproportionation reaction was 42.3 kJ/mol. The reproducibility of the experimental product distribution occurred with an average relative error of ±2%. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 555,563, 2003 [source] | ||||||||||||||||||||||||||||||||||||||||||||||