High-precision frequency measurements: indispensable tools at the core of the molecular-level analysis of complex systems

This perspective article provides an assessment of the state-of-the-art in the molecular-resolution analysis of complex organic materials. These materials can be divided into biomolecules in complex mixtures (which are amenable to successful separation into unambiguously defined molecular fractions) and complex nonrepetitive materials (which cannot be purified in the conventional sense because they are even more intricate). Molecular-level analyses of these complex systems critically depend on the integrated use of high-performance separation, high-resolution organic structural spectroscopy and mathematical data treatment. At present, only high-precision frequency-derived data exhibit sufficient resolution to overcome the otherwise common and detrimental effects of intrinsic averaging, which deteriorate spectral resolution to the degree of bulk-level rather than molecular-resolution analysis. High-precision frequency measurements are integral to the two most influential organic structural spectroscopic methods for the investigation of complex materials—NMR spectroscopy (which provides unsurpassed detail on close-range molecular order) and FTICR mass spectrometry (which provides unrivalled resolution)—and they can be translated into isotope-specific molecular-resolution data of unprecedented significance and richness. The quality of this standalone de novo molecular-level resolution data is of unparalleled mechanistic relevance and is sufficient to fundamentally advance our understanding of the structures and functions of complex biomolecular mixtures and nonrepetitive complex materials, such as natural organic matter (NOM), aerosols, and soil, plant and microbial extracts, all of which are currently poorly amenable to meaningful target analysis. The discrete analytical volumetric pixel space that is presently available to describe complex systems (defined by NMR, FT mass spectrometry and separation technologies) is in the range of 108–14 voxels, and is therefore capable of providing the necessary detail for a meaningful molecular-level analysis of very complex mixtures. Nonrepetitive complex materials exhibit mass spectral signatures in which the signal intensity often follows the number of chemically feasible isomers. This suggests that even the most strongly resolved FTICR mass spectra of complex materials represent simplified (e.g. isomer-filtered) projections of structural space

Lexical selection in action: Evidence from spontaneous punning

Analysis of a corpus of spontaneously produced Japanese puns from a single speaker over a two-year period provides a view of how a punster selects a source word for a pun and transforms it into another word for humorous effect. The pun-making process is driven by a principle of similarity: the source word should as far as possible be preserved (in terms of segmental sequence) in the pun. This renders homophones (English example: band–banned) the pun type of choice, with part–whole relationships of embedding (cap–capture), and mutations of the source word (peas–bees) rather less favored. Similarity also governs mutations in that single-phoneme substitutions outnumber larger changes, and in phoneme substitutions, subphonemic features tend to be preserved. The process of spontaneous punning thus applies, on line, the same similarity criteria as govern explicit similarity judgments and offline decisions about pun success (e.g., for inclusion in published collections). Finally, the process of spoken-word recognition is word-play-friendly in that it involves multiple word-form activation and competition, which, coupled with known techniques in use in difficult listening conditions, enables listeners to generate most pun types as offshoots of normal listening procedures

Perceived language competence modulates criteria for speech error processing: evidence from event-related potentials

With event-related potentials we examined how speaker identity affects the processing of speech errors. In two experiments with probe verification and sentence correctness judgement tasks, respectively, grammatical agreement violations and slips of the tongue were embedded in German sentences spoken in native or Chinese accent. Portraits of European or Asian persons served as cues for speaker's identity. In Experiment 1, only a P600 was elicited by grammatical agreement errors in native speech in the second presentations. In Experiment 2, grammatical errors again elicited a P600 only in native speech. Slips of the tongue, however, elicited a P600 in both native and non-native speech and a N400 for native speech. Hence, perceived speaker nativeness seems to modulate the integration of grammatical agreement violations into the utterance. Slips of the tongue induced (re)interpretation processes (P600) for both native and non-native speech, whereas retrieval of lexico-semantic information (N400) is reduced in non-native speech.Peer Reviewe