Ionic Conductivity of Nanocrystalline and Amorphous Li10GeP2S12: The Detrimental Impact of Local Disorder on Ion Transport.

Solids with extraordinarily high Li+ dynamics are key for high performance all-solid-state batteries. The thiophosphate Li10GeP2S12 (LGPS) belongs to the best Li-ion conductors with an ionic conductivity exceeding 10 mS cm-1 at ambient temperature. Recent molecular dynamics simulations performed by Dawson and Islam predict that the ionic conductivity of LGPS can be further enhanced by a factor of 3 if local disorder is introduced. As yet, no experimental evidence exists supporting this fascinating prediction. Here, we synthesized nanocrystalline LGPS by high-energy ball-milling and probed the Li+ ion transport parameters. Broadband conductivity spectroscopy in combination with electric modulus measurements allowed us to precisely follow the changes in Li+ dynamics. Surprisingly and against the behavior of other electrolytes, bulk ionic conductivity turned out to decrease with increasing milling time, finally leading to a reduction of σ20°C by a factor of 10. 31P, 6Li NMR, and X-ray diffraction showed that ball-milling forms a structurally heterogeneous sample with nm-sized LGPS crystallites and amorphous material. At -135 °C, electrical relaxation in the amorphous regions is by 2 to 3 orders of magnitude slower. Careful separation of the amorphous and (nano)crystalline contributions to overall ion transport revealed that in both regions, Li+ ion dynamics is slowed down compared to untreated LGPS. Hence, introducing defects into the LGPS bulk structure via ball-milling has a negative impact on ionic transport. We postulate that such a kind of structural disorder is detrimental to fast ion transport in materials whose transport properties rely on crystallographically well-defined diffusion pathways.

Opening Diffusion Pathways through Site Disorder: The Interplay of Local Structure and Ion Dynamics in the Solid Electrolyte Li6+xP1-xGexS5I as Probed by Neutron Diffraction and NMR.

Solid electrolytes are at the heart of future energy storage systems. Li-bearing argyrodites are frontrunners in terms of Li+ ion conductivity. Although many studies have investigated the effect of elemental substitution on ionic conductivity, we still do not fully understand the various origins leading to improved ion dynamics. Here, Li6+xP1-xGexS5I served as an application-oriented model system to study the effect of cation substitution (P5+ vs Ge4+) on Li+ ion dynamics. While Li6PS5I is a rather poor ionic conductor (10-6 S cm-1, 298 K), the Ge-containing samples show specific conductivities on the order of 10-2 S cm-1 (330 K). Replacing P5+ with Ge4+ not only causes S2-/I- anion site disorder but also reveals via neutron diffraction that the Li+ ions do occupy several originally empty sites between the Li rich cages in the argyrodite framework. Here, we used 7Li and 31P NMR to show that this Li+ site disorder has a tremendous effect on both local ion dynamics and long-range Li+ transport. For the Ge-rich samples, NMR revealed several new Li+ exchange processes, which are to be characterized by rather low activation barriers (0.1-0.3 eV). Consequently, in samples with high Ge-contents, the Li+ ions have access to an interconnected network of pathways allowing for rapid exchange processes between the Li cages. By (i) relating the changes of the crystal structure and (ii) measuring the dynamic features as a function of length scale, we were able to rationalize the microscopic origins of fast, long-range ion transport in this class of electrolytes.

Prognostic value of changes in high-sensitivity cardiac troponin T beyond biological variation in stable outpatients with cardiovascular disease: a validation study.

OBJECTIVE: To evaluate the prognostic implications of longitudinal long-term changes beyond the biological variation of high-sensitivity cardiac troponin T (hs-cTnT) in outpatients with stable or asymptomatic cardiovascular disease (CV) and to assess possible differences in the prognostic value while using reference change value (RCV) and minimal important differences (MID) as metric for biological variation. METHODS: Hs-cTnT was measured at index visit and after 12 months in outpatients presenting for routine follow-up. The prognostic relevance of a concentration change of hs-cTnT values exceeding the biological variation defined by RCV and MID of a healthy population within the next 12 months following the stable initial period was determined regarding three endpoints: all-cause mortality (EP1), a composite of all-cause mortality, non-fatal myocardial infarction and stroke (EP2), and a composite of all-cause mortality, non-fatal myocardial infarction, stroke, hospitalization for acute coronary syndrome (ACS) or decompensated heart failure, and planned and unplanned percutaneous coronary interventions (PCI, EP3). RESULTS: Change in hs-cTnT values exceeding the biovariability defined by MID but not by RCV discriminated a group with a higher cardiovascular risk profile. Changes within MID were associated with uneventful course (NPV 91.6-99.7%) while changes exceeding MID were associated with a higher occurrence of all endpoints within the next 365 days indicating a 5.5-fold increased risk for EP 1 (p = 0.041) a 2.4-fold increased risk for EP 2 (p = 0.049) and a 1.9-fold increased risk for EP 3 (p < 0.0001). CONCLUSIONS: In stable outpatients MID calculated from hs-cTnT changes measured 365 ± 120 days apart are helpful to predict an uneventful clinical course. CLINICAL TRIALS IDENTIFIER: NCT01954303.

With a Little Help from 31P NMR: The Complete Picture on Localized and Long-Range Li+ Diffusion in Li6PS5I.

Li6PS5I acts as a perfect model substance to study length scale-dependent diffusion parameters in an ordered matrix. It provides Li-rich cages which offer rapid but localized Li+ translational jump processes. As jumps between these cages are assumed to be much less frequent, long-range ion transport is sluggish, resulting in ionic conductivities in the order of 10-6 S cm-1 at room temperature. In contrast, the site disordered analogues Li6PS5X (X = Br, Cl) are known as fast ion conductors because structural disorder facilities intercage dynamics. As yet, the two extremely distinct jump processes in Li6PS5I have not been visualized separately. Here, we used a combination of 31P and 7Li NMR relaxation measurements to probe this bimodal dynamic behavior, that is, ultrafast intracage Li+ hopping and the much slower Li+ intercage exchange process. While the first is to be characterized by an activation energy of ca. 0.2 eV as directly measured by 7Li NMR, the latter is best observed by 31P NMR and follows the Arrhenius law determined by 0.44 eV. This activation energy perfectly agrees with that seen by direct current conductivity spectroscopy being sensitive to long-range ion transport for which the intercage jumps are the rate limiting step. Moreover, quantitative agreement in terms of diffusion coefficients is also observed. The solid-state diffusion coefficient D σ obtained from conductivity spectroscopy agrees very well with that from 31P NMR (D NMR ≈ 4.6 × 10-15 cm2 s-1). D NMR was directly extracted from the pronounced diffusion-controlled 31P NMR spin-lock spin-lattice relaxation peak appearing at 366 K.

Isolable Geminal Bisgermenolates: A New Synthon in Organometallic Chemistry.

We have synthesized the first isolable geminal bisenolates L2 K2 Ge[(CO)R]2 (R=2,4,6-trimethylphenyl (2 a,b), L=THF for (2 a) or [18]-crown-6 for (2 b)), a new synthon for the synthesis of organometallic reagents. The formation of these derivatives was confirmed by NMR spectroscopy and X-ray crystallographic analysis. The UV/Vis spectra of these anions show three distinct bands, which were assigned by DFT calculations. The efficiency of 2 a,b to serve as new building block in macromolecular chemistry is demonstrated by the reactions with two different types of electrophiles (acid chlorides and alkyl halides). In all cases the salt metathesis reaction gave rise to novel Ge-based photoinitiators in good yields.

Conductor-Insulator Interfaces in Solid Electrolytes: A Design Strategy to Enhance Li-Ion Dynamics in Nanoconfined LiBH4/Al2O3.

Synthesizing Li-ion-conducting solid electrolytes with application-relevant properties for new energy storage devices is a challenging task that relies on a few design principles to tune ionic conductivity. When starting with originally poor ionic compounds, in many cases, a combination of several strategies, such as doping or substitution, is needed to achieve sufficiently high ionic conductivities. For nanostructured materials, the introduction of conductor-insulator interfacial regions represents another important design strategy. Unfortunately, for most of the two-phase nanostructured ceramics studied so far, the lower limiting conductivity values needed for applications could not be reached. Here, we show that in nanoconfined LiBH4/Al2O3 prepared by melt infiltration, a percolating network of fast conductor-insulator Li+ diffusion pathways could be realized. These heterocontacts provide regions with extremely rapid 7Li NMR spin fluctuations giving direct evidence for very fast Li+ jump processes in both nanoconfined LiBH4/Al2O3 and LiBH4-LiI/Al2O3. Compared to the nanocrystalline, Al2O3-free reference system LiBH4-LiI, nanoconfinement leads to a strongly enhanced recovery of the 7Li NMR longitudinal magnetization. The fact that almost no difference is seen between LiBH4-LiI/Al2O3 and LiBH4/Al2O3 unequivocally reveals that the overall 7Li NMR spin-lattice relaxation rates are solely controlled by the spin fluctuations near or in the conductor-insulator interfacial regions. Thus, the conductor-insulator nanoeffect, which in the ideal case relies on a percolation network of space charge regions, is independent of the choice of the bulk crystal structure of LiBH4, either being orthorhombic (LiBH4/Al2O3) or hexagonal (LiBH4-LiI/Al2O3). 7Li (and 1H) NMR shows that rapid local interfacial Li-ion dynamics is corroborated by rather small activation energies on the order of only 0.1 eV. In addition, the LiI-stabilized layer-structured form of LiBH4 guarantees fast two-dimensional (2D) bulk ion dynamics and contributes to facilitating fast long-range ion transport.

Nonverbal Semantics Test (NVST)-A Novel Diagnostic Tool to Assess Semantic Processing Deficits: Application to Persons with Aphasia after Cerebrovascular Accident.

Assessment of semantic processing capacities often relies on verbal tasks which are, however, sensitive to impairments at several language processing levels. Especially for persons with aphasia there is a strong need for a tool that measures semantic processing skills independent of verbal abilities. Furthermore, in order to assess a patient's potential for using alternative means of communication in cases of severe aphasia, semantic processing should be assessed in different nonverbal conditions. The Nonverbal Semantics Test (NVST) is a tool that captures semantic processing capacities through three tasks-Semantic Sorting, Drawing, and Pantomime. The main aim of the current study was to investigate the relationship between the NVST and measures of standard neurolinguistic assessment. Fifty-one persons with aphasia caused by left hemisphere brain damage were administered the NVST as well as the Aachen Aphasia Test (AAT). A principal component analysis (PCA) was conducted across all AAT and NVST subtests. The analysis resulted in a two-factor model that captured 69% of the variance of the original data, with all linguistic tasks loading high on one factor and the NVST subtests loading high on the other. These findings suggest that nonverbal tasks assessing semantic processing capacities should be administered alongside standard neurolinguistic aphasia tests.

Tracking Ions the Direct Way: Long-Range Li+ Dynamics in the Thio-LISICON Family Li4MCh4 (M = Sn, Ge; Ch = S, Se) as Probed by 7Li NMR Relaxometry and 7Li Spin-Alignment Echo NMR.

Solid electrolytes are key elements for next-generation energy storage systems. To design powerful electrolytes with high ionic conductivity, we need to improve our understanding of the mechanisms that are at the heart of the rapid ion exchange processes in solids. Such an understanding also requires evaluation and testing of methods not routinely used to characterize ion conductors. Here, the ternary Li4MCh4 system (M = Ge, Sn; Ch = Se, S) provides model compounds to study the applicability of 7Li nuclear magnetic resonance (NMR) spin-alignment echo (SAE) spectroscopy to probe slow Li+ exchange processes. Whereas the exact interpretation of conventional spin-lattice relaxation data depends on models, SAE NMR offers a model-independent, direct access to motional correlation rates. Indeed, the jump rates and activation energies deduced from time-domain relaxometry data perfectly agree with results from 7Li SAE NMR. In particular, long-range Li+ diffusion in polycrystalline Li4SnS4 as seen by NMR in a dynamic range covering 6 orders of magnitude is determined by an activation energy of E a = 0.55 eV and a pre-exponential factor of 3 × 1013 s-1. The variation in E a and 1/τ0 is related to the LiCh4 volume that changes within the four Li4MCh4 compounds studied. The corresponding volume of Li4SnS4 seems to be close to optimum for Li+ diffusivity.

Isolable Geminal Bisgermenolates: A New Synthon in Organometallic Chemistry.

We have synthesized the first isolable geminal bisenolates L2K2Ge[(CO)R]2 (R=2,4,6-trimethylphenyl (2 a,b), L=THF for (2 a) or [18]-crown-6 for (2 b)), a new synthon for the synthesis of organometallic reagents. The formation of these derivatives was confirmed by NMR spectroscopy and X-ray crystallographic analysis. The UV/Vis spectra of these anions show three distinct bands, which were assigned by DFT calculations. The efficiency of 2 a,b to serve as new building block in macromolecular chemistry is demonstrated by the reactions with two different types of electrophiles (acid chlorides and alkyl halides). In all cases the salt metathesis reaction gave rise to novel Ge-based photoinitiators in good yields.

Evaluating Models of Gesture and Speech Production for People With Aphasia.

People with aphasia use gestures not only to communicate relevant content but also to compensate for their verbal limitations. The Sketch Model (De Ruiter, 2000) assumes a flexible relationship between gesture and speech with the possibility of a compensatory use of the two modalities. In the successor of the Sketch Model, the AR-Sketch Model (De Ruiter, 2017), the relationship between iconic gestures and speech is no longer assumed to be flexible and compensatory, but instead iconic gestures are assumed to express information that is redundant to speech. In this study, we evaluated the contradictory predictions of the Sketch Model and the AR-Sketch Model using data collected from people with aphasia as well as a group of people without language impairment. We only found compensatory use of gesture in the people with aphasia, whereas the people without language impairments made very little compensatory use of gestures. Hence, the people with aphasia gestured according to the prediction of the Sketch Model, whereas the people without language impairment did not. We conclude that aphasia fundamentally changes the relationship of gesture and speech.

The Production of Gesture and Speech by People With Aphasia: Influence of Communicative Constraints.

Purpose People with aphasia (PWA) use different kinds of gesture spontaneously when they communicate. Although there is evidence that the nature of the communicative task influences the linguistic performance of PWA, so far little is known about the influence of the communicative task on the production of gestures by PWA. We aimed to investigate the influence of varying communicative constraints on the production of gesture and spoken expression by PWA in comparison to persons without language impairment. Method Twenty-six PWA with varying aphasia severities and 26 control participants (CP) without language impairment participated in the study. Spoken expression and gesture production were investigated in 2 different tasks: (a) spontaneous conversation about topics of daily living and (b) a cartoon narration task, that is, retellings of short cartoon clips. The frequencies of words and gestures as well as of different gesture types produced by the participants were analyzed and tested for potential effects of group and task. Results Main results for task effects revealed that PWA and CP used more iconic gestures and pantomimes in the cartoon narration task than in spontaneous conversation. Metaphoric gestures, deictic gestures, number gestures, and emblems were more frequently used in spontaneous conversation than in cartoon narrations by both participant groups. Group effects show that, in both tasks, PWA's gesture-to-word ratios were higher than those for the CP. Furthermore, PWA produced more interactive gestures than the CP in both tasks, as well as more number gestures and pantomimes in spontaneous conversation. Conclusions The current results suggest that PWA use gestures to compensate for their verbal limitations under varying communicative constraints. The properties of the communicative task influence the use of different gesture types in people with and without aphasia. Thus, the influence of communicative constraints needs to be considered when assessing PWA's multimodal communicative abilities.

It takes two to pantomime: Communication meets motor cognition.

For over a century, pantomime of tool use has been employed to diagnose limb apraxia, a disorder of motor cognition primarily induced by left brain damage. While research consistently implicates damage to a left fronto-temporo-parietal network in limb apraxia, findings are inconsistent regarding the impact of damage to anterior versus posterior nodes within this network on pantomime. Complicating matters is the fact that tool use pantomime can be affected and evaluated at multiple levels. For instance, the production of tool use gestures requires the consideration of semantic characteristics (e.g. how to communicate the action intention) as well as motor features (e.g. forming grip and movement). Together, these factors may contribute substantially to apparent discrepancies in previously reported findings regarding neural correlates of tool use pantomime. In the current study, 67 stroke patients with unilateral left-brain damage performed a classic pantomime task. In order to analyze different error characteristics, we evaluated the proper use of grip and movement for each pantomime. For certain objects, healthy subjects may use body parts as representative for the object, e.g. use of the fingers to indicate scissors blades. To specify the pathological use of body parts as the object (BPO) we only assessed pantomime items that were not prone to this response in healthy participants. We performed modern voxel-based lesion analyses on MRI or CT data to determine associations between brain injury and the frequency of the specific types of pantomime errors. Our results support a model in which anterior and posterior nodes of the left fronto-temporo-parietal network contribute differentially to pantomime of tool use. More precisely, damage in the inferior frontal cortex reaching to the temporal pole is associated with an increased frequency of BPO errors, whereas damage to the inferior parietal lobe is predominantly linked to an increased frequency of movement and/or grip errors. Our work suggests that the validity of attempts to specify the neural correlates of limb apraxia based on tool use pantomime depends on differentiating the specific types of errors committed. We conclude that successful tool use pantomime involves dissociable functions with communicative aspects represented in more anterior (rather ventral) regions and motor-cognitive aspects in more posterior (rather dorsal) nodes of a left fronto-temporo-parietal network.

How Much Information Do People With Aphasia Convey via Gesture?

PURPOSE: People with aphasia (PWA) face significant challenges in verbally expressing their communicative intentions. Different types of gestures are produced spontaneously by PWA, and a potentially compensatory function of these gestures has been discussed. The current study aimed to investigate how much information PWA communicate through 3 types of gesture and the communicative effectiveness of such gestures. METHOD: Listeners without language impairment rated the information content of short video clips taken from PWA in conversation. Listeners were asked to rate communication within a speech-only condition and a gesture + speech condition. RESULTS: The results revealed that the participants' interpretations of the communicative intentions expressed in the clips of PWA were significantly more accurate in the gesture + speech condition for all tested gesture types. CONCLUSION: It was concluded that all 3 gesture types under investigation contributed to the expression of semantic meaning communicated by PWA. Gestures are an important communicative means for PWA and should be regarded as such by their interlocutors. Gestures have been shown to enhance listeners' interpretation of PWA's overall communication.

Comprehensibility and neural substrate of communicative gestures in severe aphasia.

Communicative gestures can compensate incomprehensibility of oral speech in severe aphasia, but the brain damage that causes aphasia may also have an impact on the production of gestures. We compared the comprehensibility of gestural communication of persons with severe aphasia and non-aphasic persons and used voxel based lesion symptom mapping (VLSM) to determine lesion sites that are responsible for poor gestural expression in aphasia. On group level, persons with aphasia conveyed more information via gestures than controls indicating a compensatory use of gestures in persons with severe aphasia. However, individual analysis showed a broad range of gestural comprehensibility. VLSM suggested that poor gestural expression was associated with lesions in anterior temporal and inferior frontal regions. We hypothesize that likely functional correlates of these localizations are selection of and flexible changes between communication channels as well as between different types of gestures and between features of actions and objects that are expressed by gestures.

Co-speech hand movements during narrations: What is the impact of right vs. left hemisphere brain damage?

Persons with brain damage show deviant patterns of co-speech hand movement behaviour in comparison to healthy speakers. It has been claimed by several authors that gesture and speech rely on a single production mechanism that depends on the same neurological substrate while others claim that both modalities are closely related but separate production channels. Thus, findings so far are contradictory and there is a lack of studies that systematically analyse the full range of hand movements that accompany speech in the condition of brain damage. In the present study, we aimed to fill this gap by comparing hand movement behaviour in persons with unilateral brain damage to the left and the right hemisphere and a matched control group of healthy persons. For hand movement coding, we applied Module I of NEUROGES, an objective and reliable analysis system that enables to analyse the full repertoire of hand movements independent of speech, which makes it specifically suited for the examination of persons with aphasia. The main results of our study show a decreased use of communicative conceptual gestures in persons with damage to the right hemisphere and an increased use of these gestures in persons with left brain damage and aphasia. These results not only suggest that the production of gesture and speech do not rely on the same neurological substrate but also underline the important role of right hemisphere functioning for gesture production.

Non-verbal communication in severe aphasia: influence of aphasia, apraxia, or semantic processing?

Patients suffering from severe aphasia have to rely on non-verbal means of communication to convey a message. However, to date it is not clear which patients are able to do so. Clinical experience indicates that some patients use non-verbal communication strategies like gesturing very efficiently whereas others fail to transmit semantic content by non-verbal means. Concerns have been expressed that limb apraxia would affect the production of communicative gestures. Research investigating if and how apraxia influences the production of communicative gestures, led to contradictory outcomes. The purpose of this study was to investigate the impact of limb apraxia on spontaneous gesturing. Further, linguistic and non-verbal semantic processing abilities were explored as potential factors that might influence non-verbal expression in aphasic patients. Twenty-four aphasic patients with highly limited verbal output were asked to retell short video-clips. The narrations were videotaped. Gestural communication was analyzed in two ways. In the first part of the study, we used a form-based approach. Physiological and kinetic aspects of hand movements were transcribed with a notation system for sign languages. We determined the formal diversity of the hand gestures as an indicator of potential richness of the transmitted information. In the second part of the study, comprehensibility of the patients' gestural communication was evaluated by naive raters. The raters were familiarized with the model video-clips and shown the recordings of the patients' retelling without sound. They were asked to indicate, for each narration, which story was being told and which aspects of the stories they recognized. The results indicate that non-verbal faculties are the most important prerequisites for the production of hand gestures. Whereas results on standardized aphasia testing did not correlate with any gestural indices, non-verbal semantic processing abilities predicted the formal diversity of hand gestures while apraxia predicted the comprehensibility of gesturing.