Monte Carlo phase diagram for diblock copolymer melts

A partial phase diagram is constructed for diblock copolymer melts using lattice-based Monte Carlo simulations. This is done by locating the order-disorder transition (ODT) with the aid of a recently proposed order parameter and identifying the ordered phase over a wide range of copolymer compositions (0.2 <= f <= 0.8). Consistent with experiments, the disordered phase is found to exhibit direct first-order transitions to each of the ordered morphologies. This includes the spontaneous formation of a perforated-lamellar phase, which presumably forms in place of the gyroid morphology due to finite-size and/or nonequilibrium effects. Also included in our study is a detailed examination of disordered cylinder-forming (f=0.3) diblock copolymers, revealing a substantial degree of pretransitional chain stretching and short-range order that set in well before the ODT, as observed previously in analogous studies on lamellar-forming (f=0.5) molecules. (c) 2006 American Institute of Physics.

Decoration of au and ag nanoparticles on self-assembling pseudopeptide-based nanofiber by using a short peptide as capping agent for metal nanoparticles

The surface of a nanofiber that is formed from a self-assembling pseudopeptide has been decorated by gold and silver nanoparticles that are stabilized by a dipeptide. Transmission electron microscopic images make the decoration visible. In this paper, a new strategy of mineralizing a pseudopeptide based nanofiber by gold and silver nanoparticles with use of a two-component nanografting method is described.

Formation of triple helical nanofibers using self-assembling chiral benzene-1,3,5-tricarboxamides and reversal of the nanostructure's handedness using mirror image building blocks

Intertwining triple helical nanofibers with an overall handedness have been formed from self-assembling chiral benzene-1,3,5-tricarboxamides 1, 2 and 3, whereas the achiralbenzene-1,3,5-tricarboxamide 4 upon self-association gives rise to straight nanofibers without any twist and transmission electron microscopy images of chiral compounds clearly demonstrate that the handedness of the triple helical nanofibers can be reversed by using the enantiomeric benzene-1,3,5-tricarboxamide building blocks.

The role of protecting groups in the formation of organogels through a nano-fibrillar network formed by self-assembling terminally protected tripeptides

A series of eight synthetic self-assembling terminally blocked tripeptides have been studied for gelation. Some of them form gels in various aromatic solvents including benzene, toluene, xylene, and chlorobenzene. It has been found that the protecting groups play an important role in the formation of organogels. It has been observed that, if the C-terminal has been changed from methyl ester to ethyl ester the gelation property does not change significantly (keeping the N-terminal protecting group same), while the change of the protecting group from ethyl ester to isopropyl ester completely abolishes the gelation property. Similarly, keeping the identical C-terminal protecting group (methyl ester) the results of the gelation study indicate that the substitution of N-terminal protection Boc-(tert-butyloxycarbonyl) to Cbz-(benzyloxycarbonyl) does change the gelation property insignificantly, while the change from Boc- to pivaloyl (Piv-) or acetyl (Ac-) group completely eliminates the gelation property. Morphological studies of the dried gels of two of the peptides indicate the presence of an entangled nano-fibrillar network that might be responsible for gelation. FTIR studies of the gels demonstrate that an intermolecular hydrogen bonding network is formed during gelation. Results of X-ray powder diffraction studies for these gelator peptides in different states (dried gels, gel, and bulk solids) reflected that the structure in the wet gel is distinctly different from the dried gel and solid state structures. Single crystal X-ray diffraction studies of a non-gelator peptide, which is structurally similar to the gelator molecules reveal that the peptide forms an antiparallel beta-sheet structure in crystals. (c) 2007 Elsevier Ltd. All rights reserved.

Trigonal pyramidal (CuN4)-N-I cores assembled by a family of tetradentate N-donor Schiff bases. Substituent effects on the Cu(II/I) potential

Copper(l) complexes of 1:3 condensates of tris(2-aminoethyl)amine and p-X-benzaldehydes (X = K Cl, NMe2 and NO2) of the type [Cu(ligand)]ClO4 are synthesised. The X-ray crystal structures of the copper(l) complexes with X = K, Cl and NMe2 are determined. In these complexes copper(l) is found to have trigonal pyramidal N-4 coordination sphere with the apical N forming a longer bond (2.191-2.202 Angstrom) than the trigonal ones (2.003-2.026 Angstrom). The Cu(II/I) potentials in these complexes span a range of 0.71-0.90 V vs SCE increasing linearly with the resonance component of the Hammett sigma for the para substituent X. It is concluded that trigonal pyramidal geometry is destabilising for copper(II).

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.

Wigner Transport models of the electron-phonon kinetics in quantum wires

Two quantum-kinetic models of ultrafast electron transport in quantum wires are derived from the generalized electron-phonon Wigner equation. The various assumptions and approximations allowing one to find closed equations for the reduced electron Wigner function are discussed with an emphasis on their physical relevance. The models correspond to the Levinson and Barker-Ferry equations, now generalized to account for a space-dependent evolution. They are applied to study the quantum effects in the dynamics of an initial packet of highly nonequilibrium carriers, locally generated in the wire. The properties of the two model equations are compared and analyzed.

Energetics of climate models: net energy balance and meridional enthalpy transport

We analyze the publicly released outputs of the simulations performed by climate models (CMs) in preindustrial (PI) and Special Report on Emissions Scenarios A1B (SRESA1B) conditions. In the PI simulations, most CMs feature biases of the order of 1 W m −2 for the net global and the net atmospheric, oceanic, and land energy balances. This does not result from transient effects but depends on the imperfect closure of the energy cycle in the fluid components and on inconsistencies over land. Thus, the planetary emission temperature is underestimated, which may explain the CMs' cold bias. In the PI scenario, CMs agree on the meridional atmospheric enthalpy transport's peak location (around 40°N/S), while discrepancies of ∼20% exist on the intensity. Disagreements on the oceanic transport peaks' location and intensity amount to ∼10° and ∼50%, respectively. In the SRESA1B runs, the atmospheric transport's peak shifts poleward, and its intensity increases up to ∼10% in both hemispheres. In most CMs, the Northern Hemispheric oceanic transport decreases, and the peaks shift equatorward in both hemispheres. The Bjerknes compensation mechanism is active both on climatological and interannual time scales. The total meridional transport peaks around 35° in both hemispheres and scenarios, whereas disagreements on the intensity reach ∼20%. With increased CO 2 concentration, the total transport increases up to ∼10%, thus contributing to polar amplification of global warming. Advances are needed for achieving a self-consistent representation of climate as a nonequilibrium thermodynamical system. This is crucial for improving the CMs' skill in representing past and future climate changes.

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.