Speech Prosody Serves Temporal Prediction of Language via Contextual Entrainment.

Temporal prediction assists language comprehension. In a series of recent behavioral studies, we have shown that listeners specifically employ rhythmic modulations of prosody to estimate the duration of upcoming sentences, thereby speeding up comprehension. In the current human magnetoencephalography (MEG) study on participants of either sex, we show that the human brain achieves this function through a mechanism termed entrainment. Through entrainment, electrophysiological brain activity maintains and continues contextual rhythms beyond their offset. Our experiment combined exposure to repetitive prosodic contours with the subsequent presentation of visual sentences that either matched or mismatched the duration of the preceding contour. During exposure to prosodic contours, we observed MEG coherence with the contours, which was source-localized to right-hemispheric auditory areas. During the processing of the visual targets, activity at the frequency of the preceding contour was still detectable in the MEG; yet sources shifted to the (left) frontal cortex, in line with a functional inheritance of the rhythmic acoustic context for prediction. Strikingly, when the target sentence was shorter than expected from the preceding contour, an omission response appeared in the evoked potential record. We conclude that prosodic entrainment is a functional mechanism of temporal prediction in language comprehension. In general, acoustic rhythms appear to endow language for employing the brain's electrophysiological mechanisms of temporal prediction.

Fast and Slow Rhythms of Naturalistic Reading Revealed by Combined Eye-Tracking and Electroencephalography.

Neural oscillations are thought to support speech and language processing. They may not only inherit acoustic rhythms, but might also impose endogenous rhythms onto processing. In support of this, we here report that human (both male and female) eye movements during naturalistic reading exhibit rhythmic patterns that show frequency-selective coherence with the EEG, in the absence of any stimulation rhythm. Periodicity was observed in two distinct frequency bands: First, word-locked saccades at 4-5 Hz display coherence with whole-head theta-band activity. Second, fixation durations fluctuate rhythmically at ∼1 Hz, in coherence with occipital delta-band activity. This latter effect was additionally phase-locked to sentence endings, suggesting a relationship with the formation of multi-word chunks. Together, eye movements during reading contain rhythmic patterns that occur in synchrony with oscillatory brain activity. This suggests that linguistic processing imposes preferred processing time scales onto reading, largely independent of actual physical rhythms in the stimulus.SIGNIFICANCE STATEMENT The sampling, grouping, and transmission of information are supported by rhythmic brain activity, so-called neural oscillations. In addition to sampling external stimuli, such rhythms may also be endogenous, affecting processing from the inside out. In particular, endogenous rhythms may impose their pace onto language processing. Studying this is challenging because speech contains physical rhythms that mask endogenous activity. To overcome this challenge, we turned to naturalistic reading, where text does not require the reader to sample in a specific rhythm. We observed rhythmic patterns of eye movements that are synchronized to brain activity as recorded with EEG. This rhythmicity is not imposed by the external stimulus, which indicates that rhythmic brain activity may serve as a pacemaker for language processing.

Natural infant-directed speech facilitates neural tracking of prosody.

Infants prefer to be addressed with infant-directed speech (IDS). IDS benefits language acquisition through amplified low-frequency amplitude modulations. It has been reported that this amplification increases electrophysiological tracking of IDS compared to adult-directed speech (ADS). It is still unknown which particular frequency band triggers this effect. Here, we compare tracking at the rates of syllables and prosodic stress, which are both critical to word segmentation and recognition. In mother-infant dyads (n=30), mothers described novel objects to their 9-month-olds while infants' EEG was recorded. For IDS, mothers were instructed to speak to their children as they typically do, while for ADS, mothers described the objects as if speaking with an adult. Phonetic analyses confirmed that pitch features were more prototypically infant-directed in the IDS-condition compared to the ADS-condition. Neural tracking of speech was assessed by speech-brain coherence, which measures the synchronization between speech envelope and EEG. Results revealed significant speech-brain coherence at both syllabic and prosodic stress rates, indicating that infants track speech in IDS and ADS at both rates. We found significantly higher speech-brain coherence for IDS compared to ADS in the prosodic stress rate but not the syllabic rate. This indicates that the IDS benefit arises primarily from enhanced prosodic stress. Thus, neural tracking is sensitive to parents' speech adaptations during natural interactions, possibly facilitating higher-level inferential processes such as word segmentation from continuous speech.

Gold Nanoprobes Exploring the Ice Structure in the Aqueous Dispersion of Poly(Ethylene Glycol)-Gold Hybrid Nanoparticles.

Ice structures and their formation process are fundamentally important to cryobiology, geoscience, and physical chemistry. In this work, we synthesized gold nanoprobes by grafting water-soluble polyethylene glycol (PEG) onto spherical gold nanoparticles and analyzed the structure of ice formation in the vicinity of the resulting hybrid PEG-Au nanoparticles (AuPEGNPs). Temperature-dependent in situ small-angle X-ray scattering (SAXS) indicated that AuPEGNPs, like PEG, caused the formation of bulk spherulite ice. Unlike for PEG, we observed the formation of lamellar ice with a periodicty of 4.6 nm, which is thermodynamically less stable than the bulk form. The lamellar ice formed after AuPEGNP agglomeration during cooling at -19 °C, and it remained during subsequent heating from -20 to -11 °C and melted at around -10 °C, far below the melting temperature of bulk ice. We explain different effects of AuPEGNP and free PEG on ice formation by the topological differences. The highly concentrated PEG chains on the agglomerated Au cores lead to the formation of PEG-hydrates that assemble into lamellar ice with a periodicity of 4.6 nm.

Environmental Degradation of Microplastics: How to Measure Fragmentation Rates to Secondary Micro- and Nanoplastic Fragments and Dissociation into Dissolved Organics.

Understanding the environmental fate of microplastics is essential for their risk assessment. It is essential to differentiate size classes and degradation states. Still, insights into fragmentation and degradation mechanisms of primary and secondary microplastics into micro- and nanoplastic fragments and other degradation products are limited. Here, we present an adapted NanoRelease protocol for a UV-dose-dependent assessment and size-selective quantification of the release of micro- and nanoplastic fragments down to 10 nm and demonstrate its applicability for polyamide and thermoplastic polyurethanes. The tested cryo-milled polymers do not originate from actual consumer products but are handled in industry and are therefore representative of polydisperse microplastics occurring in the environment. The protocol is suitable for various types of microplastic polymers, and the measured rates can serve to parameterize mechanistic fragmentation models. We also found that primary microplastics matched the same ranking of weathering stability as their corresponding macroplastics and that dissolved organics constitute a major rate of microplastic mass loss. The results imply that previously formed micro- and nanoplastic fragments can further degrade into water-soluble organics with measurable rates that enable modeling approaches for all environmental compartments accessible to UV light.

Effect of Polymer Properties on the Biodegradation of Polyurethane Microplastics.

The release of fragments from plastic products, that is, secondary microplastics, is a major concern in the context of the global plastic pollution. Currently available (thermoplastic) polyurethanes [(T)PU] are not biodegradable and therefore should be recycled. However, the ester bond in (T)PUs might be sufficiently hydrolysable to enable at least partial biodegradation of polyurethane particles. Here, we investigated biodegradation in compost of different types of (T)PU to gain insights into their fragmentation and biodegradation mechanisms. The studied (T)PUs varied regarding the chemistry of their polymer backbone (aromatic/aliphatic), hard phase content, cross-linking degree, and presence of a hydrolysis-stabilizing additive. We developed and validated an efficient and non-destructive polymer particle extraction process for partially biodegraded (T)PUs based on ultrasonication and density separation. Our results showed that biodegradation rates and extents decreased with increasing cross-linking density and hard-segment content. We found that the presence of a hydrolysis stabilizer reduced (T)PU fragmentation while not affecting the conversion of (T)PU carbon into CO2. We propose a biodegradation mechanism for (T)PUs that includes both mother particle shrinkage by surface erosion and fragmentation. The presented results help to understand structure-degradation relationships of (T)PUs and support recycling strategies.

Endogenous Oscillations Time-Constrain Linguistic Segmentation: Cycling the Garden Path.

Speech is transient. To comprehend entire sentences, segments consisting of multiple words need to be memorized for at least a while. However, it has been noted previously that we struggle to memorize segments longer than approximately 2.7 s. We hypothesized that electrophysiological processing cycles within the delta band (<4 Hz) underlie this time constraint. Participants' EEG was recorded while they listened to temporarily ambiguous sentences. By manipulating the speech rate, we aimed at biasing participants' interpretation: At a slow rate, segmentation after 2.7 s would trigger a correct interpretation. In contrast, at a fast rate, segmentation after 2.7 s would trigger a wrong interpretation and thus an error later in the sentence. In line with the suggested time constraint, the phase of the delta-band oscillation at the critical point in the sentence mirrored segmentation on the level of single trials, as indicated by the amplitude of the P600 event-related brain potential (ERP) later in the sentence. The correlation between upstream delta-band phase and downstream P600 amplitude implies that segmentation took place when an underlying neural oscillator had reached a specific angle within its cycle, determining comprehension. We conclude that delta-band oscillations set an endogenous time constraint on segmentation.

A Deep Eutectic Solvent Thermomorphic Multiphasic System for Biocatalytic Applications.

The applicability of a thermomorphic multiphasic system (TMS) composed of a hydrophobic deep eutectic solvent (DES) and an aqueous potassium phosphate buffer with a lower critical solution temperature (LCST) phase change for homogeneous biocatalysis was investigated. A lidocaine-based DES with the fatty acid oleic acid as a hydrogen-bond donor was studied. Phase diagrams were determined and presented within this study. We tested different additional components to the solvent system and observed a decrease in the cloud point of approximately 0.026 °C per concentration unit. Distribution studies revealed a clear distribution of the protein in the aqueous buffer phase (>95 %), whereas the hydrophobic substrate and educt accumulated (>95 %) in the DES-enriched layer. Finally, a reduction catalyzed by horse liver alcohol dehydrogenase was performed in a larger-scale experiment, and the biocatalyst could be recycled by simply removing the DES phase for three recycling runs.

Application of In Situ Product Crystallization and Related Techniques in Biocatalytic Processes.

This Minireview highlights the application of crystallization as a very powerful in situ product removal (ISPR) technique in biocatalytic process design. Special emphasis is placed on its use for in situ product crystallization (ISPC) to overcome unfavorable thermodynamic reaction equilibria, inhibition, and undesired reactions. The combination of these unit operations requires an interdisciplinary perspective to find a holistic solution for the underlying bioprocess intensification approach. Representative examples of successful integrated process options are selected, presented, and assessed regarding their overall productivity and applicability. In addition, parallels to the use of adsorption as a very similar technique are drawn and similarities discussed.