One Cue's Loss Is Another Cue's Gain-Learning Morphophonology Through Unlearning.

A word often expresses many different morphological functions. Which part of a word contributes to which part of the overall meaning is not always clear, which raises the question as to how such functions are learned. While linguistic studies tacitly assume the co-occurrence of cues and outcomes to suffice in learning these functions (Baer-Henney, Kügler, & van de Vijver, 2015; Baer-Henney & van de Vijver, 2012), error-driven learning suggests that contingency rather than contiguity is crucial (Nixon, 2020; Ramscar, Yarlett, Dye, Denny, & Thorpe, 2010). In error-driven learning, cues gain association strength if they predict a certain outcome, and they lose strength if the outcome is absent. This reduction of association strength is called unlearning. So far, it is unclear if such unlearning has consequences for cue-outcome associations beyond the ones that get reduced. To test for such consequences of unlearning, we taught participants morphophonological patterns in an artificial language learning experiment. In one block, the cues to two morphological outcomes-plural and diminutive-co-occurred within the same word forms. In another block, a single cue to only one of these two outcomes was presented in a different set of word forms. We wanted to find out, if participants unlearn this cue's association with the outcome that is not predicted by the cue alone, and if this allows the absent cue to be associated with the absent outcome. Our results show that if unlearning was possible, participants learned that the absent cue predicts the absent outcome better than if no unlearning was possible. This effect was stronger if the unlearned cue was more salient. This shows that unlearning takes place even if no alternative cues to an absent outcome are provided, which highlights that learners take both positive and negative evidence into account-as predicted by domain general error-driven learning.

Reduced syntactic recursion in spontaneous speech of Parkinson's disease patients.

Although characterized as a movement disorder, Parkinson's disease (PD) affects more than just the motor system. Within the heterogenous non-motor symptoms, language impairment is frequent but poorly understood beyond semantic processing. This study investigates the impact of PD on syntactic subordination in spontaneous language production. Fifteen PD patients in ON levodopa status narrated a short story guided by a set of pictures. Thirteen PD patients were also assessed in OFF levodopa status. Narrations were digitally recorded, subsequently transcribed and annotated, making the produced speech accessible to systematical quantitative analysis. Compared to a healthy matched control group, PD patients showed a significant reduction of subordinating structures while the number of non-embedding sentences remained unaffected. No significant effect comparing ON versus OFF levodopa status emerged. Our results suggest a contribution of the basal ganglia to language processing, such as syntactic composition, which, however, does not seem to be dopamine dependent.

Learning new words via feedback-Association between feedback-locked ERPs and recall performance-An exploratory study.

Feedback learning is thought to involve the dopamine system and its projection sites in the basal ganglia and anterior cingulate cortex (ACC), regions associated with procedural learning. Under certain conditions, such as when feedback is delayed, feedback-locked activation is pronounced in the medial temporal lobe (MTL), which is associated with declarative learning. In event-related potential research, the feedback-related negativity (FRN) has been linked to immediate feedback processing, while the N170, possibly reflecting MTL activity, has been related to delayed feedback processing. In the current study, we performed an exploratory investigation on the relation between N170 and FRN amplitude and memory performance in a test for declarative memory (free recall), also exploring the role of feedback delay. To this end, we adapted a paradigm in which participants learned associations between non-objects and non-words with either immediate or delayed feedback, and added a subsequent free recall test. We indeed found that N170, but not FRN amplitudes, depended on later free recall performance, with smaller amplitudes for later remembered non-words. In an additional analysis with memory performance as dependent variable, the N170, but not the FRN amplitude predicted free recall, modulated by feedback timing and valence. This finding shows that the N170 reflects an important process during feedback processing, possibly related to expectations and their violation, but is distinct from the process reflected by the FRN.

Automated Reaction Kinetics of Gas-Phase Organic Species over Multiwell Potential Energy Surfaces.

Automation of rate-coefficient calculations for gas-phase organic species became possible in recent years and has transformed how we explore these complicated systems computationally. Kinetics workflow tools bring rigor and speed and eliminate a large fraction of manual labor and related error sources. In this paper we give an overview of this quickly evolving field and illustrate, through five detailed examples, the capabilities of our own automated tool, KinBot. We bring examples from combustion and atmospheric chemistry of C-, H-, O-, and N-atom-containing species that are relevant to molecular weight growth and autoxidation processes. The examples shed light on the capabilities of automation and also highlight particular challenges associated with the various chemical systems that need to be addressed in future work.

New Perspectives into Cellulose Fast Pyrolysis Kinetics Using a Py-GC × GC-FID/MS System.

Cellulose pyrolysis is reportedly influenced by factors such as sample size, crystallinity, or different morphologies. However, there seems to be a lack of understanding of the mechanistic details that explain the observed differences in the pyrolysis yields. This study aims to investigate the influence of particle size and crystallinity of cellulose by performing pyrolysis reactions at temperatures of 673-873 K using a micropyrolyzer apparatus coupled to a GC × GC-FID/TOF-MS and a customized GC-TCD. Over 60 product species have been identified and quantified for the first time, including water. Crystalline cellulose with an average particle size of 30-50 × 10-6 m produced 50-60 wt % levoglucosan. Predominantly amorphous cellulose with an average particle size of 10-20 × 10-6 m resulted in remarkably low yields (10-15 wt %) of levoglucosan complemented by higher yields of water and glycolaldehyde. A detailed kinetic model for cellulose pyrolysis was used to obtain mechanistic insights into the different pyrolysis product compositions. The kinetics of the mid-chain dehydration and fragmentation reactions strongly influence the total yields of low-molecular weight products (LMWPs) and are affected by cellulose chain arrangement. Levoglucosan yields are very sensitive to the activation of parallel cellulose decomposition reactions. This can be attributed to the mid-chain reactions forming smaller chains with the levoglucosan ends, which remain in the solid phase and react further to form LMWPs. Direct quantification of water helped to improve the description of the dehydration, giving further indications of the dominant role of mid-chain reaction pathways in amorphous cellulose pyrolysis.

The merit of pressure dependent kinetic modelling in steam cracking.

Renewable cracking feedstocks from plastic waste and the need for novel reactor designs related to electrification of steam crackers drives the development of accurate and fundamental kinetic models for this process, despite its large scale implementation for more than half a century. Pressure dependent kinetics have mostly been omitted in fundamental steam cracking models, while they are crucial in combustion models. Therefore, we have assessed the importance of pressure dependent kinetics for steam cracking via in-depth modelling and experimental studies. In particular we have studied the influence of considering fall-off on the product yields for ethane and propane steam cracking. A high-pressure limit fundamental kinetic model is generated, based on quantum chemical data and group additive values, and supplemented with literature values for pressure dependent kinetic parameters for ß-scission reactions and homolytic bond scissions of C2 and C3 species. Model simulations with high-pressure limit rate coefficients and pressure dependent kinetics are compared to new experimental measurements. Steam cracking experiments for pure ethane and propane feeds are performed on a tubular bench-scale reactor at 0.17 MPa and temperatures ranging from 1058 to 1178 K. All important product species are identified using a comprehensive GC × GC-FID/q-MS. For homolytic bond scissions, the inclusion of pressure dependent kinetics has a significant effect on the conversion profile for ethane steam cracking. On the other hand, pressure dependence of C2 ß-scissions significantly influences conversion and product species profiles for both ethane and propane steam cracking. The C3 ß-scissions pressure dependence has a negligible effect in ethane steam cracking, while for propane steam cracking the effect is non-negligible on the product species profiles.

Learning Molecular Representations for Thermochemistry Prediction of Cyclic Hydrocarbons and Oxygenates.

Accurate thermochemistry estimation of polycyclic molecules is crucial for kinetic modeling of chemical processes that use renewable and alternative feedstocks. In kinetic model generators, molecular properties are estimated rapidly with group additivity, but this method is known to have limitations for polycyclic structures. This issue has been resolved in our work by combining a geometry-based molecular representation with a deep neural network trained on ab initio data. Each molecule is transformed into a probabilistic vector from its interatomic distances, bond angles, and dihedral angles. The model is tested on a small experimental dataset (200 molecules) from the literature, a new medium-sized set (4000 molecules) with both open-shell and closed-shell species, calculated at the CBS-QB3 level with empirical corrections, and a large G4MP2-level QM9-based dataset (40 000 molecules). Heat capacities between 298.15 and 2500 K are calculated in the medium set with an average deviation of about 1.5 J mol-1 K-1 and the standard entropy at 298.15 K is predicted with an average error below 4 J mol-1 K-1. The standard enthalpy of formation at 298.15 K has an average out-of-sample error below 4 kJ mol-1 on a QM9 training set size of around 15 000 molecules. By fitting NASA polynomials, the enthalpy of formation at higher temperatures can be calculated with the same accuracy as the standard enthalpy of formation. Uncertainty quantification by means of the ensemble standard deviation is included to indicate when molecules that are on the edge or outside of the application range of the model are evaluated.

Deep Brain Stimulation Does Not Modulate Auditory-Motor Integration of Speech in Parkinson's Disease.

Deep brain stimulation (DBS) has significant effects on motor symptoms in Parkinson's disease (PD), but existing studies on the effect of DBS on speech are rather inconclusive. It is assumed that deficits in auditory-motor integration strongly contribute to Parkinsonian speech pathology. The aim of the present study was to assess whether subthalamic DBS can modulate these deficits. Twenty PD patients (15 male, 5 female; 62.4 ± 6.7 years) with subthalamic DBS were exposed to pitch-shifted acoustic feedback during vowel vocalization and subsequent listening. Voice and brain activity were measured ON and OFF stimulation using magnetoencephalography (MEG). Vocal responses and auditory evoked responses time locked to the onset of pitch-shifted feedback were examined. A positive correlation between vocal response magnitude and pitch variability was observed for both, stimulation ON and OFF (ON: r = 0.722, p < 0.001, OFF: r = 0.746, p < 0.001). However, no differences of vocal responses to pitch-shifted feedback between the stimulation conditions were found [t (19) = -0.245, p = 0.809, d = -0.055]. P200m amplitudes of event related fields (ERF) of left and right auditory cortex (AC) and superior temporal gyrus (STG) were significantly larger during listening [left AC P200m: F (1, 19) = 10.241, p = 0.005, f = 0.734; right STG P200m: F (1, 19) = 8.393, p = 0.009, f = 0.664]. Subthalamic DBS appears to have no substantial effect on vocal compensations, although it has been suggested that auditory-motor integration deficits contribute to higher vocal response magnitudes in pitch perturbation experiments with PD patients. Thus, DBS seems to be limited in modulating auditory-motor integration of speech in PD.

The Influence of Orthography on Phonemic Knowledge: An Experimental Investigation on German and Persian.

This study investigated whether the phonological representation of a word is modulated by its orthographic representation in case of a mismatch between the two representations. Such a mismatch is found in Persian, where short vowels are represented phonemically but not orthographically. Persian adult literates, Persian adult illiterates, and German adult literates were presented with two auditory tasks, an AX-discrimination task and a reversal task. We assumed that if orthographic representations influence phonological representations, Persian literates should perform worse than Persian illiterates or German literates on items with short vowels in these tasks. The results of the discrimination tasks showed that Persian literates and illiterates as well as German literates were approximately equally competent in discriminating short vowels in Persian words and pseudowords. Persian literates did not well discriminate German words containing phonemes that differed only in vowel length. German literates performed relatively poorly in discriminating German homographic words that differed only in vowel length. Persian illiterates were unable to perform the reversal task in Persian. The results of the other two participant groups in the reversal task showed the predicted poorer performance of Persian literates on Persian items containing short vowels compared to items containing long vowels only. German literates did not show this effect in German. Our results suggest two distinct effects of orthography on phonemic representations: whereas the lack of orthographic representations seems to affect phonemic awareness, homography seems to affect the discriminability of phonemic representations.

Ab initio derived group additivity model for intramolecular hydrogen abstraction reactions.

A set of group additivity values for intramolecular hydrogen abstraction reactions of alkanes, alkenes and alkynes is reported. Calculating 448 reaction rate coefficients at the CBS-QB3 level of theory for 1-2 up to 1-7 hydrogen shift reactions allowed the estimation of ΔGAV° values for 270 groups. The influence of substituents on (1) the attacking radical, (2) the attacked carbon atom, and (3) the carbon chain between the attacking and attacked reactive atom has been systematically studied. Substituents have been varied between hydrogen atoms and sp3, sp2 and sp hybridized carbon atoms. It has been assumed that substituents further away from the reactive atoms or their connecting carbon chain have negligible influences on the kinetics. This group additivity model is applicable to a wide variety of reactions in the 300-1800 K temperature range. Correlations for tunneling coefficients have been generated which are complementary to the ΔGAV°'s to obtain accurate rate coefficients without the need for imaginary frequencies or electronic energies of activation. These correlations depend on the temperature and activation energy of the exothermic step. The group additivity model has been successfully applied to a test set of reactions also calculated at the CBS-QB3 level of theory. A mean absolute deviation of 1.18 to 1.71 has been achieved showing a good overall accuracy of the model.

Symmetry calculation for molecules and transition states.

The symmetry of molecules and transition states of elementary reactions is an essential property with important implications for computational chemistry. The automated identification of symmetry by computers is a very useful tool for many applications, but often relies on the availability of three-dimensional coordinates of the atoms in the molecule and hence becomes less useful when these coordinates are a priori unavailable. This article presents a new algorithm that identifies symmetry of molecules and transition states based on an augmented graph representation of the corresponding structures, in which both topology and the presence of stereocenters are accounted for. The automorphism group order of the graph associated with the molecule or transition state is used as a starting point. A novel concept of label-stereoisomers, that is, stereoisomers that arise after labeling homomorph substituents in the original molecule so that they become distinguishable, is introduced and used to obtain the symmetry number. The algorithm is characterized by its generic nature and avoids the use of heuristic rules that would limit the applicability. The calculated symmetry numbers are in agreement with expected values for a large and diverse set of structures, ranging from asymmetric, small molecules such as fluorochlorobromomethane to highly symmetric structures found in drug discovery assays. The new algorithm opens up new possibilities for the fast screening of the degree of symmetry of large sets of molecules.

The Interaction of Language-Specific and Universal Factors During the Acquisition of Morphophonemic Alternations With Exceptions.

Using the artificial language paradigm, we studied the acquisition of morphophonemic alternations with exceptions by 160 German adult learners. We tested the acquisition of two types of alternations in two regularity conditions while additionally varying length of training. In the first alternation, a vowel harmony, backness of the stem vowel determines backness of the suffix. This process is grounded in substance (phonetic motivation), and this universal phonetic factor bolsters learning a generalization. In the second alternation, tenseness of the stem vowel determines backness of the suffix vowel. This process is not based in substance, but it reflects a phonotactic property of German and our participants benefit from this language-specific factor. We found that learners use both cues, while substantive bias surfaces mainly in the most unstable situation. We show that language-specific and universal factors interact in learning.

Developing biases.

German nouns may alternate from singular to plural in two different ways. Some singular forms that end in a voiceless obstruent have a plural in which this obstruent is voiced. Another alternation concerns the vowel. Some singular forms with a back vowel have a plural form in which this back vowel is front. For each noun it has to be established individually whether it alternates or not. The voicing alternation is phonetically grounded, but the vowel alternation is not. Knowledge about such alternations involves two things. First, it involves knowledge of which words alternate and which words do not and second, it involves the ability to extend the alternations to novel words. We studied the knowledge of which words alternate and the proportion to which they alternate in two corpus studies. We studied the knowledge of speakers concerning which words alternate and what generalizations can be based upon these words by means of a production study. The production study involved words and nonces. We asked twenty 5 year-olds, twenty 7 year-olds, and ten adults to produce the plural for a given singular word and a plural for a given singular nonce. In the corpus study we found that both alternations occur with the same frequency. In the production of alternations in words we found that participants in all age groups make few mistakes. With respect to the production of alternations in nonce words, we found that the proportion of voicing alternations decreases with age, while the proportion of vowel alternations increases. We explain this change in the ability to generalize the alternations to nonces on the basis of the confidence speakers can have in a generalization. Young children have a small lexicon and they can form relatively unreliable generalizations on lexical distributions. They are, however, proficient users of language and have great phonetic experience. They can more confidently form generalizations on the basis of this experience. Adults have a large lexicon and, as a consequence, they can confidently form generalizations based on their lexicon. In addition, they know that many alternations are not based on phonetic considerations.