Observation of carbonyl oxygen-pi interaction in a metal complex

X-ray crystallography shows that [Ag2L2(H2O)(2)](BF4)(2) where L is a 1:1 condensate of 1,2-diphenylethane-1,2-dione and 2-(2-aminoethyl pyridine), contains an Ag(I)-Ag(I) bond of length 2.979(2) angstrom and an angular, intraligand interaction of the keto O with the pi cloud of the pyridine moiety (O-pyridine centroid = 3.12 angstrom). Model MP2/6-311++G(d,p) calculations indicate that the observed lone pair-pi type interaction is stabilising and not merely a tolerated short contact. (C) 2008 Elsevier B.V. All rights reserved.

A monoaqua zinc complex. Unique acid dissociation behaviour

Using the I : 2 condensate of benzil dihydrazone and 2-acetylpyridine as the ligand L, two complexes of zinc, [ZnL(CH3COO)]PF6 (1) and [ZnL(H2O)CIO4]CIO4 H2O (2), are synthesised from Zn(CH3COO)(2).2H(2)O and Zn(CIO4)(2).6H(2)O, respectively. From X-ray crystallography, both the complexes are found to be single helical with the metal in distorted octahedral N4O2 environment. In 1, the two oxygen atoms come from the bidentate acetate while 2 is a monoaqua complex with a perchlorate anion bound to the metal in monodentate fashion. The perchlorate in 2 is not at all weakly bound [Zn-O(perchlorate) 2.256(4) A]. Still in acetonitrile solution, the coordinated perchlorate ion dissociates upon deprotonation [reaction (i)].

An eight-coordinate mononuclear double helical complex

From the reaction of Cd(CH3COO)(2)(.)2H(2)O with the 1:2 condensate (L) of benzil dihydrazone and 2-acetylpyridine, [CdL(CH3COO)(H2O)]PF(6)(.)3H(2)O (1) is isolated by adding NH4PF6. L reacts with Cd(ClO4)(2)(.)xH(2)O to yield [CdL2](ClO4)(2). 0.5H(2)O (2). The yellowish complexes 1 and 2 are characterized by NMR and single-crystal X-ray diffraction. 1 is found to be a seven-coordinate single helical complex having a (CdN4O3)-N-II core and homoleptic 2 an eight-coordinate double helical complex with a (CdN8)-N-II core. (c) Wiley-VCH Verlag GmbH & Co.

Zinc(II) mediated synthesis of an N-substituted 2-(2-pyridyl)imidazole from a 1,2-diketone and 2-(aminomethyl)pyridine and its ligational behaviour

Reaction of anhydrous ZnCl2 with the 1:2 condensate (L) of benzil and 2-(aminomethyl)pyridine in methanol gives monomeric ZnL'Cl-2 (1) where L' is 2-[(4,5-diphenyl-2-pyridin-2-yl-1H-imidazol-1-yl)-methyl]pyridine. In the X-ray crystal structure, 1 is found to contain tetrahedral zinc with an N2Cl2 coordination sphere and the N-substituent methylpyridine fragment hanging as a free arm. A tentative mechanism is proposed for the zinc mediated conversion of L-->L'. Demetallation of 1 by the action of aqueous NaOH yields L' in the free state. When L' is reacted with Zn(ClO4)(2).6H(2)O in a 1:2 molar proportion, [Zn(L')(2)](n)(ClO4)(2n).(H2O)(n/2).(CH2Cl2)(n/2) (2) is obtained. The zinc atom in 2, as revealed by X-ray crystallography, has a trigonal bipyramidal N-5 coordination sphere. There are two independent ligands in the asymmetric unit of 2. One of them bonds only to one zinc atom in a bidentate mode with the N-substituent methylpyridine hanging free while the other ligand binds to two different zinc atoms in a tridentate fashion, employing the N-substituent methylpyridine nitrogen atom to form the polymeric one-dimensional chain cation.

Mixed ligand binuclear copper(I) complexes containing (Cu2N8)-N-I chromophores. Observation of emissions from MLCT excited states involving two different ligands

Using the 1:2 condensate (L) of diethylenetriamine and benzaldehyde as the main ligand, binuclear copper(l) complexes [Cu2L2(4,4'-bipyridine)](CIO4)(2).0.5H(2)O (1a) and [Cu2L2(1,2-bis(4-pyridyl)ethane)](CIO4)(2) (1b) are synthesised. The two metal ions in la are bridged by 4,4'-bipyridine and those in 1b by 1,2-bis(4-pyridyl)ethane, From the X-ray crystal structure of la, each metal ion is found to be bound to three N atoms of L and one of the two N atoms of the bridging ligand in a distorted tetrahedral fashion. The Cu(I)-N bond lengths in la lie in the range of 1.998(5)-2.229(6) Angstrom. Electrochemical studies in dichloromethane (DCM) show that the (Cu2N8)-N-I moieties in la and 1b are composed of two essentially non-interacting (CuN4)-N-I cores with Cu-II/I potential of 0.44 V vs. SCE. While la displays metal induced quenching of the inherent emission of 4,4'-bipyridine in DCM solution, 1b exhibits two weak emission bands in DCM solution at 425 and 477 nm (total quantum yield = 3.59 x 10(-5)) originating from MLCT excited states. With the help of Extended Huckel calculations it is established that the higher energy emission in 1b is from Cu(I) --> bridging-ligand charge transfer excited state and the lower energy one in 1b from Cu(I) --> L charge transfer excited state.

Conceptual and perceptual processing in prospective remembering

McDaniel, Robinson-Riegler, and Einstein (1998) recently reported findings in support of the proposal that prospective remembering is largely conceptually driven. In each of the three experiments they reported, however, the task in which the prospective memory target was encountered at test had a predominantly conceptual focus, thereby potentially facilitating retrieval of conceptually encoded features of the studied target event. We report two experiments in which we manipulated the dimension (perceptual or conceptual) along which a target event varied between study and test while using a processing task, at both study and test, compatible with the relevant dimension of target change. When the target was encountered in a sentence validity task at study and test, and the semantic context in which a target was encountered was changed between these two occasions, prospective remembering declined (Experiment 1). A similar decline occurred, using a readability rating task, when the perceptual context (font in which the word was printed) was altered (Experiment 2). These results indicate that both perceptual and conceptual processes can support prospective remembering.

Mesonic fluctuations in a nonlocal Nambu–Jona-Lasinio model

The effects of meson fluctuations are studied in a nonlocal generalization of the Nambu–Jona-Lasinio model, by including terms of next-to-leading order (NLO) in 1/Nc. In the model with only scalar and pseudoscalar interactions NLO contributions to the quark condensate are found to be very small. This is a result of cancellation between virtual mesons and Fock terms, which occurs for the parameter sets of most interest. In the quark self-energy, similar cancellations arise in the tadpole diagrams, although not in other NLO pieces which contribute at the 25% level. The effects on pion properties are also found to be small. NLO contributions from real pi-pi intermediate states increase the sigma meson mass by 30%. In an extended model with vector and axial interactions, there are indications that NLO effects could be larger.

Mononuclear single helices of lanthanum(III) and europium(III). Metal dependent diastereomeric excess

Using the 1: 2 condensate of benzildihydrazone and 2-acetylpyridine as a tetradentate N donor ligand L, LaL(NO3)(3) (1) and EuL(NO3)(3) (2), which are pale yellow in colour, are synthesized. While single crystals of 1 could not be obtained, 2 crystallises as a monodichloromethane solvate, 2 center dot CH2Cl2 in the space group Cc with a = 11.7099(5) angstrom, b = 16.4872(5) angstrom, c = 17.9224(6) angstrom and beta = 104.048(4)degrees. From the X-ray crystal structure, 2 is found to be a rare example of monohelical complex of Eu(III). Complex 1 is diamagnetic. The magnetic moment of 2 at room temperature is 3.32 BM. Comparing the FT-IR spectra of 1 and 2, it is concluded that 1 also is a mononuclear single helix. H-1 NMR reveals that both 1 and 2 are mixtures of two diastereomers. In the case of the La(III) complex (1), the diastereomeric excess is only 10% but in the Eu(III) complex 2 it is 80%. The occurrence of diastereomerism is explained by the chiralities of the helical motif and the type of pentakis chelates present in 1 and 2.

Effect of phonetic complexity on word reading and repetition in deep dyslexia

This investigation moves beyond the traditional studies of word reading to identify how the production complexity of words affects reading accuracy in an individual with deep dyslexia (JO). We examined JO’s ability to read words aloud while manipulating both the production complexity of the words and the semantic context. The classification of words as either phonetically simple or complex was based on the Index of Phonetic Complexity. The semantic context was varied using a semantic blocking paradigm (i.e., semantically blocked and unblocked conditions). In the semantically blocked condition words were grouped by semantic categories (e.g., table, sit, seat, couch,), whereas in the unblocked condition the same words were presented in a random order. JO’s performance on reading aloud was also compared to her performance on a repetition task using the same items. Results revealed a strong interaction between word complexity and semantic blocking for reading aloud but not for repetition. JO produced the greatest number of errors for phonetically complex words in semantically blocked condition. This interaction suggests that semantic processes are constrained by output production processes which are exaggerated when derived from visual rather than auditory targets. This complex relationship between orthographic, semantic, and phonetic processes highlights the need for word recognition models to explicitly account for production processes.

Age-related changes in the functional neuroanatomy of overt speech production

Alterations of existing neural networks during healthy aging, resulting in behavioral deficits and changes in brain activity, have been described for cognitive, motor, and sensory functions. To investigate age-related changes in the neural circuitry underlying overt non-lexical speech production, functional MRI was performed in 14 healthy younger (21–32 years) and 14 healthy older individuals (62–84 years). The experimental task involved the acoustically cued overt production of the vowel /a/ and the polysyllabic utterance /pataka/. In younger and older individuals, overt speech production was associated with the activation of a widespread articulo-phonological network, including the primary motor cortex, the supplementary motor area, the cingulate motor areas, and the posterior superior temporal cortex, similar in the /a/ and /pataka/ condition. An analysis of variance with the factors age and condition revealed a significant main effect of age. Irrespective of the experimental condition, significantly greater activation was found in the bilateral posterior superior temporal cortex, the posterior temporal plane, and the transverse temporal gyri in younger compared to older individuals. Significantly greater activation was found in the bilateral middle temporal gyri, medial frontal gyri, middle frontal gyri, and inferior frontal gyri in older vs. younger individuals. The analysis of variance did not reveal a significant main effect of condition and no significant interaction of age and condition. These results suggest a complex reorganization of neural networks dedicated to the production of speech during healthy aging.

Measuring quality of life in aphasia: results from two scales

Background: Although aphasia affects quality of life (QoL), the impact within specific domains (e.g., psychosocial, communication) is poorly understood. Moreover, the complex and multidimensional nature of QoL renders it difficult to measure accurately using a single global scale. Aims: Using two recently developed QoL scales, the Stroke and Aphasia Quality of Life Scale-39, (SAQOL; Hilari, Byng, Lamping, & Smith, 2003a) and the American Speech Language Hearing Association’s Quality of Communication Life Scale (QCL; Paul et al., 2004), this study aimed to document the domains of QoL that were most affected for participants with aphasia compared to control participants, as well as to determine the relationship between the two scales, their sub-domains, and linguistic variables in aphasia. Methods & Procedures: The two scales were administered to a group of 19 participants with aphasia (14 male, 5 female), ages ranging from 27 to 79 years, and 19 age- and gender-matched control participants. Various types and severity of aphasia were represented in the aphasia group. The performances of aphasia and control groups were compared, and correlation analyses examined the relationship between the two scales and their sub-domains in the aphasia group only. Outcomes & Results: Compared to control participants, QoL was lower in participants with aphasia, with the communication sub-domain of SAQOL and socialisation/ activities sub-domain of QCL being the most affected areas of functioning. Between the two scales, the communication sub-domain of SAQOL correlated with the socialisation/ activities sub-domain and the QCL mean. Moreover, linguistic variables correlated strongly with psychosocial, communication and socialisation/activities sub-domains of QoL. Conclusions: Measuring QoL using the SAQOL and the QCL captures different but equally important aspects of experiences of living with aphasia. When interpreted together, they provide a holistic picture of functioning in aphasia that includes broad overviews of QoL from the SAQOL and a finer-grained analysis of communication impairments on QoL from the QCL.

Effects of utterance length on lip kinematics in aphasia

Most existing models of language production and speech motor control do not explicitly address how language requirements affect speech motor functions, as these domains are usually treated as separate and independent from one another. This investigation compared lip movements during bilabial closure between five individuals with mild aphasia and five age and gender-matched control speakers when the linguistic characteristics of the stimuli were varied by increasing the number of syllables. Upper and lower lip movement data were collected for mono-, bi- and tri-syllabic nonword sequences using an AG 100 EMMA system. Each task was performed under both normal and fast rate conditions. Single articulator kinematic parameters (peak velocity, amplitude, duration,and cyclic spatio-temporal index) were measured to characterize lip movements. Results revealed that compared to control speakers, individuals with aphasia showed significantly longer movement duration and lower movement stability for longer items (bi- and tri-syllables). Moreover, utterance length affected the lip kinematics, in that the monosyllables had smaller peak velocities, smaller amplitudes and shorter durations compared to bi- and trisyllables, and movement stability was lowest for the trisyllables. In addition, the rate-induced changes (smaller amplitude and shorter duration with increased rate) were most prominent for the short items (i.e., monosyllables). These findings provide further support for the notion that linguistic changes have an impact on the characteristics of speech movements, and that individuals with aphasia are more affected by such changes than control speakers.

Word frequency and bigram frequency effects on linguistic processing and speech motor performance in individuals with aphasia and normal speakers

Models of normal word production are well specified about the effects of frequency of linguistic stimuli on lexical access, but are less clear regarding the same effects on later stages of word production, particularly word articulation. In aphasia, this lack of specificity of down-stream frequency effects is even more noticeable because there is relatively limited amount of data on the time course of frequency effects for this population. This study begins to fill this gap by comparing the effects of variation of word frequency (lexical, whole word) and bigram frequency (sub-lexical, within word) on word production abilities in ten normal speakers and eight mild–moderate individuals with aphasia. In an immediate repetition paradigm, participants repeated single monosyllabic words in which word frequency (high or low) was crossed with bigram frequency (high or low). Indices for mapping the time course for these effects included reaction time (RT) for linguistic processing and motor preparation, and word duration (WD) for speech motor performance (word articulation time). The results indicated that individuals with aphasia had significantly longer RT and WD compared to normal speakers. RT showed a significant main effect only for word frequency (i.e., high-frequency words had shorter RT). WD showed significant main effects of word and bigram frequency; however, contrary to our expectations, high-frequency items had longer WD. Further investigation of WD revealed that independent of the influence of word and bigram frequency, vowel type (tense or lax) had the expected effect on WD. Moreover, individuals with aphasia differed from control speakers in their ability to implement tense vowel duration, even though they could produce an appropriate distinction between tense and lax vowels. The results highlight the importance of using temporal measures to identify subtle deficits in linguistic and speech motor processing in aphasia, the crucial role of phonetic characteristics of stimuli set in studying speech production and the need for the language production models to account more explicitly for word articulation.

Speech motor control in fluent and dysfluent speech production of an individual with apraxia of speech and Broca’s aphasia

Apraxia of speech (AOS) is typically described as a motor-speech disorder with clinically well-defined symptoms, but without a clear understanding of the underlying problems in motor control. A number of studies have compared the speech of subjects with AOS to the fluent speech of controls, but only a few have included speech movement data and if so, this was primarily restricted to the study of single articulators. If AOS reflects a basic neuromotor dysfunction, this should somehow be evident in the production of both dysfluent and perceptually fluent speech. The current study compared motor control strategies for the production of perceptually fluent speech between a young woman with apraxia of speech (AOS) and Broca’s aphasia and a group of age-matched control speakers using concepts and tools from articulation-based theories. In addition, to examine the potential role of specific movement variables on gestural coordination, a second part of this study involved a comparison of fluent and dysfluent speech samples from the speaker with AOS. Movement data from the lips, jaw and tongue were acquired using the AG-100 EMMA system during the reiterated production of multisyllabic nonwords. The findings indicated that although in general kinematic parameters of fluent speech were similar in the subject with AOS and Broca’s aphasia to those of the age-matched controls, speech task-related differences were observed in upper lip movements and lip coordination. The comparison between fluent and dysfluent speech characteristics suggested that fluent speech was achieved through the use of specific motor control strategies, highlighting the potential association between the stability of coordinative patterns and movement range, as described in Coordination Dynamics theory.