Recognition of sequence-information in synthetic copolymer chains by a conformationally-constrained tweezer molecule

A novel type of tweezer molecule containing electron-rich 2-pyrenyloxy arms has been designed to exploit intramolecular hydrogen bonding in stabilising a preferred conformation for supramolecular complexation to complementary sequences in aromatic copolyimides. This tweezer-conformation is demonstrated by single-crystal X-ray analyses of the tweezer molecule itself and of its complex with an aromatic diimide model-compound. In terms of its ability to bind selectively to polyimide chains, the new tweezer molecule shows very high sensitivity to sequence effects. Thus, even low concentrations of tweezer relative to diimide units (<2.5 mol%) are sufficient to produce dramatic, sequence-related splittings of the pyromellitimide proton NMR resonances. These induced resonance-shifts arise from ring-current shielding of pyromellitimide protons by the pyrenyloxy arms of the tweezer-molecule, and the magnitude of such shielding is a function of the tweezer-binding constant for any particular monomer sequence. Recognition of both short-range and long-range sequences is observed, the latter arising from cumulative ring-current shielding of diimide protons by tweezer molecules binding at multiple adjacent sites on the copolymer chain.

Principles of sequence-recognition in aromatic polyimides

Pyrene-based molecular tweezers show sequence-specific binding to aromatic polyimides through sterically-controlled donor-acceptor pi-stacking and hydrogen bonding; H-1 NMR spectra of tweezer-complexes with polyimides having different sequence-restrictions show conclusively that the detection of long range sequence-information results from multiple tweezer-binding at adjacent imide residues.

A direct comparison of one- and two-component dendritic self-assembled materials: elucidating molecular recognition pathways

This paper compares and contrasts, for the first time, one- and two-component gelation systems that are direct structural analogues and draws conclusions about the molecular recognition pathways that underpin fibrillar self-assembly. The new one-component systems comprise L-lysine-based dendritic headgroups covalently connected to an aliphatic diamine spacer chain via an amide bond, One-component gelators with different generations of headgroup (from first to third generation) and different length spacer chains are reported. The self-assembly of these dendrimers in toluene was elucidated using thermal measurements, circular dichroism (CD) and NMR spectroscopies, scanning electron microscopy (SEM), and small-angle X-ray scattering (SAXS). The observations are compared with previous results for the analogous two-component gelation system in which the dendritic headgroups are bound to the aliphatic spacer chain noncovalently via acid-amine interactions. The one-component system is inherently a more effective gelator, partly as a consequence of the additional covalent amide groups that provide a new hydrogen bonding molecular recognition pathway, whereas the two-component analogue relies solely on intermolecular hydrogen bond interactions between the chiral dendritic headgroups. Furthermore, because these amide groups are important in the assembly process for the one-component system, the chiral information preset in the dendritic headgroups is not always transcribed into the nanoscale assembly, whereas for the two-component system, fiber formation is always accompanied by chiral ordering because the molecular recognition pathway is completely dependent on hydrogen bond interactions between well-organized chiral dendritic headgroups.

Ditopic redox-active polyferrocenyl zinc(II) dithiocarbamate macrocyclic receptors: synthesis, coordination and electrochemical recognition properties

The synthesis of a range of ditopic polyferrocenyl zinc(II) dithiocarbamate macrocyclic receptors containing ferrocene groups on the macrocycle's periphery and/or as part of the cyclic cavity is reported. The assemblies have been characterised by a range of spectroscopic techniques, electrochemical studies and in two cases by X-ray structure determination. The ability of these host systems to bind and sense electrochemically anionic guest species, isonicotinate and benzoate, and neutral 4-picoline guest was examined by H-1 NMR and cyclic voltammetric titration studies. The strongest association was found between the isonicotinate anion and a dinuclear zinc(II) receptor whose macrocyclic cavity is of complementary size to complex this bidentate guest species in a cooperative manner. Cyclic voltammetric studies demonstrated that all receptors can electrochemically sense the binding of isonicotinate and benzoate via significant cathodic perturbations of the respective ferrocene redox couple.

Utilisation of dendritic architectures in molecular recognition and self-assembly processes

This mini-review outlines recent key developments in the use of dendritic architectures in self-assembly processes via utilisation of molecular recognition motifs.

Development of a method fon non-destructive testing of fruits using scanning laser vibrometry (SLV)

Quality control on fruits requires reliable methods, able to assess with reasonable accuracy and possibly in a non-destructive way their physical and chemical characteristics. More specifically, a decreased firmness indicates the presence of damage or defects in the fruit or else that the fruit has exceeded its “best before date”, becoming unsuitable for consumption. In high-value exotic fruits, such as mangoes, where firmness cannot be easily measured from a simple observation of texture, colour changes and unevenness of fruits surface, the use of non-destructive techniques is highly recommendable. In particular, the application of Laser vibrometry, based on the Doppler effect, a non-contact technique sensitive to differences in displacements inferior to the nanometre, appears ideal for a possible on-line control on food. Previous results indicated that a phase shift can be in a repeatable way associated with the presence of damage on the fruit, whilst a decreased firmness results in significant differences in the displacement of the fruits under the same excitation signal. In this work, frequency ranges for quality control via the application of a sound chirp are suggested, based on the measurement of the signal coherence. The variations of the average vibration spectrum of a grid of points, or of point-by-point signal velocity allows the go-no go recognition of “firm” and “over-ripe” fruits, with notable success in the particular case of mangoes. The future exploitation of this work will include the application of this method to allow on-line control during conveyor belt distribution of fruits.

The relationship between phonological awareness and word reading accuracy in Oriya and English: A Study of Oriya-speaking fifth-graders

This study investigated the relationships between phonological awareness and reading in Oriya and English. Oriya is the official language of Orissa, an eastern state of India. The writing system is an alphasyllabary. Ninety-nine fifth grade children (mean age 9 years 7 months) were assessed on measures of phonological awareness, word reading and pseudo-word reading in both languages. Forty-eight of the children attended Oriya-medium schools where they received literacy instruction in Oriya from grade 1 and learned English from grade 2. Fifty-one children attended English-medium schools where they received literacy instruction in English from grade 1 and in Oriya from grade 2. The results showed that phonological awareness in Oriya contributed significantly to reading Oriya and English words and pseudo-words for the children in the Oriya-medium schools. However, it only contributed to Oriya pseudo-word reading and English word reading for children in the English-medium schools. Phonological awareness in English contributed to English word and pseudo-word reading for both groups. Further analyses investigated the contribution of awareness of large phonological units (syllable, onsets and rimes) and small phonological units (phonemes) to reading in each language. The data suggest that cross-language transfer and facilitation of phonological awareness to word reading is not symmetrical across languages and may depend both on the characteristics of the different orthographies of the languages being learned and whether the first literacy language is also the first spoken language.

The relative success of recognition-based inference in multichoice decisions

The utility of an "ecologically rational" recognition-based decision rule in multichoice decision problems is analyzed, varying the type of judgment required (greater or lesser). The maximum size and range of a counterintuitive advantage associated with recognition-based judgment (the "less-is-more effect") is identified for a range of cue validity values. Greater ranges of the less-is-more effect occur when participants are asked which is the greatest of to choices (m > 2) than which is the least. Less-is-more effects also have greater range for larger values of in. This implies that the classic two-altemative forced choice task, as studied by Goldstein and Gigerenzer (2002), may not be the most appropriate test case for less-is-more effects.

False recognition of abstract versus common objects in older and younger adults: testing the semantic categorization account

Older adults often demonstrate higher levels of false recognition than do younger adults. However, in experiments using novel shapes without preexisting semantic representations, this age-related elevation in false recognition was found to be greatly attenuated. Two experiments tested a semantic categorization account of these findings, examining whether older adults show especially heightened false recognition if the stimuli have preexisting semantic representations, such that semantic category information attenuates or truncates the encoding or retrieval of item-specific perceptual information. In Experiment 1, ambiguous shapes were presented with or without disambiguating semantic labels. Older adults showed higher false recognition when labels were present but not when labels were never presented. In Experiment 2, older adults showed higher false recognition for concrete but not abstract objects. The semantic categorization account was supported.

Quantitative analysis of accuracy of an inertial/acoustic 6DOF tracking system in motion

An increasing number of neuroscience experiments are using virtual reality to provide a more immersive and less artificial experimental environment. This is particularly useful to navigation and three-dimensional scene perception experiments. Such experiments require accurate real-time tracking of the observer's head in order to render the virtual scene. Here, we present data on the accuracy of a commonly used six degrees of freedom tracker (Intersense IS900) when it is moved in ways typical of virtual reality applications. We compared the reported location of the tracker with its location computed by an optical tracking method. When the tracker was stationary, the root mean square error in spatial accuracy was 0.64 mm. However, we found that errors increased over ten-fold (up to 17 mm) when the tracker moved at speeds common in virtual reality applications. We demonstrate that the errors we report here are predominantly due to inaccuracies of the IS900 system rather than the optical tracking against which it was compared. (c) 2006 Elsevier B.V. All rights reserved.

Rich and famous: recognition-based judgment in the Sunday Times rich list

Recognition as a cue to judgment in a novel, multi-option domain (the Sunday Times Rich List) is explored. As in previous studies, participants were found to make use of name recognition as a cue to the presumed wealth of individuals. Names that were recognized were judged to be the richest name from amongst the set presented at above chance levels. This effect persisted across situations in which more than one name was recognized; recognition was used as an inclusion criterion for the sub-set of names to be considered the richest of the set presented. However, when the question was reversed, and a “poorest” judgment was required, use of recognition as an exclusion criterion was observed only when a single name was recognized. Reaction times when making these judgments also show a distinction between “richest” and “poorest” questions with recognition of none of the options taking the longest time to judge in the “richest” question condition and full recognition of all the names presented taking longest to judge in the “poorest” question condition. Implications for decision-making using simple heuristics are discussed.

An analysis of real time implementation of Fourier transform-based frequency recognition algorithms

Frequency recognition is an important task in many engineering fields such as audio signal processing and telecommunications engineering, for example in applications like Dual-Tone Multi-Frequency (DTMF) detection or the recognition of the carrier frequency of a Global Positioning, System (GPS) signal. This paper will present results of investigations on several common Fourier Transform-based frequency recognition algorithms implemented in real time on a Texas Instruments (TI) TMS320C6713 Digital Signal Processor (DSP) core. In addition, suitable metrics are going to be evaluated in order to ascertain which of these selected algorithms is appropriate for audio signal processing(1).