The Interplay of Spacer Chirality and Parity in Mesogenic Dimers.

Introducing chirality into soft materials, including liquid crystals (LCs), profoundly impacts their self-organization and physical properties. In this study, we synthesized a novel series of LC dimers with a chiral center as part of their flexible spacer. The dimers were prepared in racemic and enantiomerically pure forms. Their spacer length and parity were varied to investigate the effect of spacer chirality and parity on mesomorphic behavior and on chiral induction in the nematic phase of achiral mesogens. Our results show that the even-membered chiral dimers only have chiral nematic phases. In contrast, the odd-membered dimers display rich mesomorphism, including the intriguing blue phase (BP) and chiral form of the twist-bend nematic phase (N*TB ). The observed significant difference in the 3D surface morphology between the racemic and chiral forms of the N*TB phase suggests that the chiral moiety in the spacer promotes a chiral hierarchy. Furthermore, the chiral dimers show a prominent odd-even effect in the helical twisting power in nematic hosts. These findings highlight the importance of the position of the chiral group within the dimeric molecule and provide new insights into how intrinsic chirality in the spacer affects the overall structural chirality.

The shared and unique neural correlates of personal semantic, general semantic, and episodic memory.

One of the most common distinctions in long-term memory is that between semantic (i.e., general world knowledge) and episodic (i.e., recollection of contextually specific events from one's past). However, emerging cognitive neuroscience data suggest a surprisingly large overlap between the neural correlates of semantic and episodic memory. Moreover, personal semantic memories (i.e., knowledge about the self and one's life) have been studied little and do not easily fit into the standard semantic-episodic dichotomy. Here, we used fMRI to record brain activity while 48 participants verified statements concerning general facts, autobiographical facts, repeated events, and unique events. In multivariate analysis, all four types of memory involved activity within a common network bilaterally (e.g., frontal pole, paracingulate gyrus, medial frontal cortex, middle/superior temporal gyrus, precuneus, posterior cingulate, angular gyrus) and some areas of the medial temporal lobe. Yet the four memory types differentially engaged this network, increasing in activity from general to autobiographical facts, from autobiographical facts to repeated events, and from repeated to unique events. Our data are compatible with a component process model, in which declarative memory types rely on different weightings of the same elementary processes, such as perceptual imagery, spatial features, and self-reflection.

Crystalline restacking of 2D-materials from their nanosheets suspensions.

We report here the highly ordered restacking of the layered phosphatoantimonic dielectric materials H3(1-x)M3xSb3P2O14, (where M = Li, Na, K, Rb, Cs and 0 ≤ x ≤ 1), from their nanosheets dispersed in colloidal suspension, induced by a simple pH change using alkaline bases. H3Sb3P2O14 aqueous suspensions are some of the rare examples of colloidal suspensions based on 2D materials exhibiting a lamellar liquid crystalline phase. Because the lamellar period can reach several hundred nanometers, the suspensions show vivid structural colors and because these colors are sensitive to various chemicals, the suspensions can be used as sensors. The structures of the lamellar liquid crystalline phase and the restacked phase have been studied by X-ray scattering (small and wide angle), which has followed the dependence of the lamellar/restacked phase equilibrium on the cation exchange rate, x. The X-ray diffraction pattern of the restacked phase is almost identical to that of the M3Sb3P2O14 crystalline phase, showing that the restacking is highly accurate and avoids the turbostratic disorder of the nanosheets classically observed in nanosheet stacking of other 2D materials. Strikingly, the restacking process exhibits features highly reminiscent of a first-order phase transition, with the existence of a phase coexistence region where both ∼1 nm (interlayer spacing of the restacked phase) and ∼120 nm lamellar periods can be observed simultaneously. Furthermore, this first-order phase transition is well described theoretically by incorporating a Lennard-Jones-type lamellar interaction potential into an entropy-based statistical physics model of the lamellar phase of nanosheets. Our work shows that the precise cation exchange produced at room temperature by a classical neutralization reaction using alkaline bases leads to a crystal-like restacking of the exfoliated free Sb3P2O143- nanosheets from suspension, avoiding the turbostratic disorder typical of van der Waals 2D materials, which is detrimental to the controlled deposition of nanosheets into complex integrated electronic, spintronic, photonic or quantum structures.

Charge-driven liquid-crystalline behavior of ligand-functionalized nanorods in apolar solvent.

Concentrated colloidal suspensions of nanorods often exhibit liquid-crystalline (LC) behavior. The transition to a nematic LC phase, with long-range orientational order of the particles, is usually well-captured by Onsager's theory for hard rods, at least qualitatively. The theory shows how the volume fraction at the transition decreases with increasing aspect ratio of the rods. It also explains that the long-range electrostatic repulsive interaction occurring between rods stabilized by their surface charge can significantly increase their effective diameter, resulting in a decrease in the volume fraction at the transition, as compared to sterically stabilized rods. Here, we report on a system of ligand-stabilized LaPO4 nanorods, of aspect ratio ≈ 11, dispersed in apolar medium exhibiting the counter-intuitive observation that the onset of nematic self-assembly occurs at an extremely low volume fraction of ≈ 0.25%, which is lower than observed (≈ 3%) with the same particles when charged-stabilized in polar solvent. Furthermore, the nanorod volume fraction at the transition increases with increasing concentration of ligands, in a similar way as in polar media where increasing the ionic strength leads to surface charge screening. This peculiar system was investigated by dynamic light scattering, Fourier-transform infrared spectroscopy, zetametry, electron microscopy, polarized light microscopy, photoluminescence measurements, and X-ray scattering. Based on these experimental data, we formulate several tentative scenarios that might explain this unexpected phase behavior. However, at this stage, its full understanding remains a pending theoretical challenge. Nevertheless, this study shows that dispersing anisotropic nanoparticles in an apolar solvent may sometimes lead to spontaneous ordering events that defy our intuitive ideas about colloidal systems.

Executive function and episodic memory composite scores in older adults: relations with sex, mood, and subjective sleep quality.

Executive function and episodic memory processes are particularly vulnerable to aging. We sought to learn the degree to which sex, mood, and subjective sleep quality might be related to executive function and episodic memory composite scores in community-dwelling older adults. We replicated Glisky and colleagues' two-factor (i.e., executive function [N=263] versus episodic memory [N=151]) structure, and found that it did not significantly differ between males and females. Moderation analyses revealed no interactions between sex, mood, and sleep in predicting either composite score. However, females significantly outperformed males on the episodic memory composite, and on all the individual tests comprising it. Ours is the first study to look at sex differences in this battery's factor structure and its potential relations with mood and sleep. Future longitudinal studies in both healthy and clinical populations will help us further probe the possible influence of these variables on executive function and episodic memory in aging.

Executive Function Predicts Older Adults' Lure Discrimination Difficulties on the Mnemonic Similarity Task.

OBJECTIVES: Older adults often have difficulty remembering the details of recently encountered objects. We previously found this with the Mnemonic Similarity Task (MST). Surprisingly, the older adults' MST Lure Discrimination Index (LDI) was significantly correlated with visual acuity but not with memory or executive function. Here we ran a replication with new, larger samples of young (N = 45) and older adults (N = 70). We then combined the original and replication older adult samples (N = 108) to critically examine the relative contributions of visual acuity, memory, and executive function composite scores to LDI performance using dominance analysis. This provided, to our knowledge, the first direct statistical comparison of all 3 of these factors and their interactions on LDI. METHODS: Participants completed the MST and a battery assessing visual acuity, memory, and executive function. We examined age group differences on MST performance in the new (i.e., replication) young and older adult samples and performed multiple regression and dominance analysis on the combined older adult sample. RESULTS: Consistent with previous findings, the older adults showed significantly poorer LDI but preserved item recognition. LDI was significantly correlated with both memory and executive function but not with visual acuity. In the combined older adult sample, all 3 composites predicted LDI, but dominance analysis indicated that executive function was the most important predictor. DISCUSSION: Older adults' MST LDI difficulty may be predicted by their executive function and visual acuity. These factors should be considered when interpreting older adults' MST performance.

A view of the pan-genome of domesticated Cowpea (Vigna unguiculata [L.] Walp.).

Cowpea, Vigna unguiculata L. Walp., is a diploid warm-season legume of critical importance as both food and fodder in sub-Saharan Africa. This species is also grown in Northern Africa, Europe, Latin America, North America, and East to Southeast Asia. To capture the genomic diversity of domesticates of this important legume, de novo genome assemblies were produced for representatives of six subpopulations of cultivated cowpea identified previously from genotyping of several hundred diverse accessions. In the most complete assembly (IT97K-499-35), 26,026 core and 4963 noncore genes were identified, with 35,436 pan genes when considering all seven accessions. GO terms associated with response to stress and defense response were highly enriched among the noncore genes, while core genes were enriched in terms related to transcription factor activity, and transport and metabolic processes. Over 5 million single nucleotide polymorphisms (SNPs) relative to each assembly and over 40 structural variants >1 Mb in size were identified by comparing genomes. Vu10 was the chromosome with the highest frequency of SNPs, and Vu04 had the most structural variants. Noncore genes harbor a larger proportion of potentially disruptive variants than core genes, including missense, stop gain, and frameshift mutations; this suggests that noncore genes substantially contribute to diversity within domesticated cowpea.

Mental rotation, episodic memory, and executive control: Possible effects of biological sex and oral contraceptive use.

Oral contraceptives (OCs) are one of the most common forms of hormonal birth control. A small literature suggests that OC use may affect visuospatial ability, episodic memory, and executive control. However, previous studies have been criticized for small sample sizes and the use of different, single cognitive tests. We investigated the degree to which biological sex and OC use might affect individual mental rotation, episodic memory, and executive control in a large sample of healthy, young adults (N = 155, including 52 OC users, 53 naturally cycling females, and 50 males) tested individually over videoconference. To measure cognition, we used a set of neuropsychological tasks inspired by Glisky and colleagues' two-factor episodic memory and executive control battery, from which two composite scores (based on principal component analysis) were derived for each participant. Our pre-registered analysis revealed a clear female advantage in episodic memory, independent of OC use. In an exploratory analysis, gist memory was elevated in OC users. Interestingly, we found no significant sex-related differences nor effects of OC use on mental rotation or executive control. Duration of OC use was also not related to any of our cognitive measures. These results suggest that the use of combined, monophasic OCs does not lead to many significant changes in cognition in young adults, although young females overall may have better episodic memory than young males. Additional studies, including longitudinal designs and looking in more detail at the menstrual cycle and OC use history, will further clarify the effects of different types of OCs and their duration of use on different aspects of cognition.

Do Aqueous Suspensions of Smectite Clays Form a Smectic Liquid-Crystalline Phase?

Bottom-up strategies for the production of well-defined nanostructures often rely on the self-assembly of anisotropic colloidal particles (nanowires and nanosheets). These building blocks can be obtained by delamination in a solvent of low-dimensionality crystallites. To optimize particle availability, determination of the delamination mechanism and the different organization stages of anisotropic particles in dispersion is essential. We address this fundamental issue by exploiting a recently developed system of fluorohectorite smectite clay mineral that delaminates in water, leading to colloidal dispersions of single-layer, very large (≈20 µm) clay sheets at high dilution. We show that when the clay crystallites are dispersed in water, they swell to form periodic one-dimensional stacks of fluorohectorite sheets with very low volume fraction (<1%) and therefore huge (≈100 nm) periods. Using optical microscopy and synchrotron X-ray scattering, we establish that these colloidal stacks bear strong similarities, yet subtle differences, with a smectic liquid-crystalline phase. Despite the high dilution, the colloidal stacks of sheets, called colloidal accordions, are extremely robust mechanically and can persist for years. Moreover, when subjected to AC electric fields, they rotate as solid bodies, which demonstrates their outstanding internal cohesion. Furthermore, our theoretical model captures the dependence of the stacking period on the dispersion concentration and ionic strength and explains, invoking the Donnan effect, why the colloidal accordions are kinetically stable over years and impervious to shear and Brownian motion. Because our model is not system specific, we expect that similar colloidal accordions frequently appear as an intermediate state during the delamination process of two-dimensional crystals in polar solvents.

Disentangling Aging and Mood Effects on Emotional Memory.

Older adults tend to be in a more positive mood than young adults, and tend to remember positive information more often than negative information, yet the link between their positive mood and their positive memory bias has not often been explored. In this study, we manipulated young and older adults' moods prior to their completing an emotional memory task. For mood manipulation, young (n = 147) and older (n = 111) adults viewed a positive, negative, or neutral video lasting 3 min. To validate the mood induction, we collected self-reported ratings of valence and arousal (affective slider; Betella and Verschure, 2016) at baseline, after the video, and after the memory task. The memory task consisted of incidental encoding of 30 intermixed pictures (10 positive, 10 negative, 10 neutral valence), followed by free recall. The mood manipulation changed people's self-reported valence, yet it did not influence self-reported arousal. The memory task revealed a consistent negativity bias in young adults. Older adults recalled negative and positive pictures equally well in all conditions. After viewing a negative video, they recalled positive pictures more often than neutral pictures, but did not show the same advantage for negative pictures over neutral pictures. This positive memory advantage was weaker in the positive mood condition. Therefore, mood manipulation influenced in part older adults' emotional memory bias, showing some signs of mood incongruence which we discuss in terms of emotion regulation. This shows the importance of accounting for mood differences in studies on aging and memory. The robust age group differences support the view that the positivity effect in aging is the result of a negativity bias that fades with age.

Older adults' episodic memory is related to a neurophysiological marker of brain cholinergic activity.

Episodic memory is vulnerable to aging and may be influenced by age-related decline in the neurotransmitter acetylcholine. We probed this relation using a novel, minimally invasive transcranial magnetic stimulation marker of brain acetylcholine: short-latency afferent inhibition (SAI). We used neuropsychological testing to construct a composite score of episodic memory in N = 19 community-dwelling older adults, and stratified older adults into Higher- (N = 9) versus Lower-memory (N = 10) groups before SAI. The Higher-memory group showed significantly stronger SAI than the Lower-memory group, indicating an association between higher brain acetylcholine levels and better episodic memory. The two memory groups were equivalent in the potential confounds of age, education, mood, subjective sleep quality, and executive function. These data converge with others to suggest that episodic memory is related to acetylcholine in older adults. This relation should be further investigated, especially with pharmacology and neuroimaging.

Lyotropic Liquid-Crystalline Phases of Sophorolipid Biosurfactants.

Biological amphiphiles derived from natural resources are presently being investigated in the hope that they will someday replace current synthetic surfactants, which are known pollutants of soils and water resources. Sophorolipids constitute one of the main classes of glycosylated biosurfactants that have attracted interest because they are synthesized by non-pathogenic yeasts from glucose and vegetable oils at high titers. In this work, the self-assembly properties of several sophorolipids in water at high concentrations (20-80 wt %), a range so far mostly uncharted, have been investigated by polarized-light microscopy and X-ray scattering. Some of these compounds were found to show lyotropic liquid-crystalline behavior as they display lamellar or hexagonal columnar mesophases. X-ray scattering data shows that the structure of the lamellar phase is almost fully interdigitated, which is likely due to the packing difference between the bulky hydrophilic tails and the more compact aliphatic chains. A tentative representation of the molecular organization of the columnar phase is also given. Moreover, some of these compounds display thermotropic liquid-crystalline behavior, either pure or in aqueous mixtures. In addition, small domains of the lamellar phase can easily be aligned by applying onto them a moderate a.c. electric field, which is a rather unusual feature for lyotropic liquid crystals. Altogether, our work explored the self-assembly liquid-crystalline behavior of sophorolipids at high concentration, which could shed light on the conditions of their potential industrial applications as well as on their biological function.

Amygdala but not hippocampal damage associated with smaller social network size.

Social network size has been associated with complex socio-cognitive processes (e.g., memory, perspective taking). Supporting this idea, recent neuroimaging studies in healthy adults have reported a relationship between social network size and brain volumes in regions related to memory and social cognition (e.g., hippocampus, amygdala). Lesion-deficit studies in neurological patients are rare and have been inconclusive due to differences in participant sampling and measurement. The present study uses a multiple case study approach. We investigated patients with focal damage to the hippocampus and/or amygdala (two neural structures thought to be critical for social networks), and examined the patients' social network size, loneliness, and life satisfaction relative to a non-injured comparison group. Patients with amygdalar damage had smaller social networks and reported higher levels of loneliness and lower life satisfaction, on average, than comparison participants. Patients with damage to the hippocampus reported more friends than the comparison participants, but did not differ in their ratings of loneliness or life satisfaction. This lesion study offers new evidence that the amygdala is critical for social networks, life satisfaction, and reduced loneliness.

The ERP correlates of self-knowledge in ageing.

Self-knowledge is a type of personal semantic knowledge that concerns one's self-image and personal identity. It has most often been operationalized as the summary of one's personality traits ("I am a stubborn person"). Interestingly, recent studies have revealed that the neural correlates of self-knowledge can be dissociated from those of general semantic and episodic memory in young adults. However, studies of "dedifferentiation" or loss of distinctiveness of neural representations in ageing suggest that the neural correlates of self-knowledge might be less distinct from those of semantic and episodic memory in older adults. We investigated this question in an event-related potential (ERP) study with 28 young and 26 older adults while they categorised personality traits for their self-relevance (self-knowledge conditions), and their relevance to certain groups of people (general semantic condition). Participants then performed a recognition test for previously seen traits (episodic condition). The amplitude of the late positive component (LPC), associated with episodic recollection processes, differentiated the self-knowledge, general semantic, and episodic conditions in young adults, but not in older adults. However, in older adults, participants with higher composite episodic memory scores had more differentiated LPC amplitudes across experimental conditions. Moreover, consistent with the fact that age-related neural dedifferentiation may be material and region specific, in both age groups some differences between memory types were observed for the N400 component, associated with semantic processing. Taken together, these findings suggest that declarative memory subtypes are less distinct in ageing, but that the amount of differentiation varies with episodic memory function.

Fine tuning the structural colours of photonic nanosheet suspensions by polymer doping.

Aqueous suspensions of nanosheets are readily obtained by exfoliating low-dimensional mineral compounds like H3Sb3P2O14. The nanosheets self-organize, at low concentration, into a periodic stack of membranes, i.e. a lamellar liquid-crystalline phase. Due to the dilution, this stack has a large period of a few hundred nanometres, it behaves as a 1-dimensional photonic material and displays structural colours. We experimentally investigated the dependence of the period on the nanosheet concentration. We theoretically showed that it cannot be explained by the usual DLVO interaction between uniform lamellae but that the particulate nature of nanosheet-laden membranes must be considered. Moreover, we observed that adding small amounts of 100 kDa poly(ethylene oxide) (PEO) decreases the period and allows tuning the colour throughout the visible range. PEO adsorbs on the nanosheets, inducing a strong reduction of the nanosheet charge. This is probably due to the Lewis-base character of the EO units of PEO that become protonated at the low pH of the system, an interpretation supported by theoretical modeling. Oddly enough, adding small amounts of 1 MDa PEO has the opposite effect of increasing the period, suggesting the presence of an additional intermembrane repulsion not yet identified. From an applied perspective, our work shows how the colours of these 1-dimensional photonic materials can easily be tuned not only by varying the nanosheet concentration (which might entail a phase transition) but also by adding PEO. From a theoretical perspective, our approach represents a necessary step towards establishing the phase diagram of aqueous suspensions of charged nanosheets.

Gold-clay nanocomposite colloids with liquid-crystalline and plasmonic properties.

Imparting liquid-crystal (LC) materials with the plasmonic properties of metal nanoparticles is actively pursued for applications. We achieved this goal by synthetizing gold nanoparticles onto clay nanosheets, leading to nematic nanocomposite suspensions. Optical observations and structural analysis show the growth of the gold nanoparticles without altering the LC properties of the nanosheets. These colloids display plasmonic structural colours and they can be aligned by an electric field, which is relevant for fundamental and materials chemistry of colloidal LC.

Correction: Solution self-assembly of plasmonic Janus nanoparticles.

Correction for 'Solution self-assembly of plasmonic Janus nanoparticles' by Nicolò Castro et al., Soft Matter, 2016, 12, 9666-9673, DOI: .

A discourse-theoretic approach to story recall in aging and mild cognitive impairment.

Recall of story materials is a primary way to assess episodic memory. However, the standard scoring method may not be maximally sensitive to cognitive decline. We developed a set of 24 stories, and younger and older adults heard these stories and recalled them immediately and after a delay (Study 1). Twelve of these stories were then selected, and older adults and people with MCI completed immediate and delayed recall of these stories (Study 2). Responses were classified as veridical, gist, or distorted, and were scored by number of units and number of propositions recalled. Younger adults had higher veridical recall than older adults, and proposition-based scoring revealed higher gist recall in older than younger adults. Gist and distortion recall increased over time in older adults, but decreased in MCI. Using proposition-based scoring and distinguishing between veridical and gist responses may discriminate better between healthy older adults and people with MCI.

Identification of residues important for M. tuberculosis MmpL11 function reveals that function is modulated by phosphorylation in the C-terminal domain.

The Mycobacterium tuberculosis cell envelope is a critical interface between the host and pathogen and provides a protective barrier against the immune response and antibiotics. Cell envelope lipids are also mycobacterial virulence factors that influence the host immune response. The mycobacterial membrane protein large (MmpL) proteins transport cell envelope lipids and siderophores that are important for the basic physiology and pathogenesis of M. tuberculosis. We recently identified MmpL11 as a conserved transporter of mycolic acid-containing lipids including monomeromycolyl diacylglycerol (MMDAG), mycolate wax ester (MWE), and long-chain triacylglycerols (LC-TAGs). These lipids contribute to biofilm formation in M. tuberculosis and M. smegmatis, and non-replicating persistence in M. tuberculosis. In this report, we identified domains and residues that are essential for MmpL11TB lipid transporter activity. Specifically, we show that the D1 periplasmic loop and a conserved tyrosine are essential for the MmpL11 function. Intriguingly, we found that MmpL11 levels are regulated by the phosphorylation of threonine in the cytoplasmic C-terminal domain, providing the first direct evidence of the phospho-regulation of MmpL11 transporter activity in M. tuberculosis and M. smegmatis. Our results offer further insight into the function of MmpL transporters and regulation of mycobacterial cell envelope biogenesis.

Destabilization of the Nematic Phase of Clay Nanosheet Suspensions by Polymer Adsorption.

Complex aqueous mixtures comprised of swelling clays and hydrosoluble polymers naturally occur in soils and play a major role in pedogenesis. They are also very often used for formulating oil-well drilling fluids, paints, and personal-care products. The suspensions of some natural clays, thanks to their large nanoparticle aspect ratio, spontaneously form nematic liquid-crystalline phases where the particles align parallel to each other, which affects their flow properties. We observed that adding small amounts of hydrosoluble polymers to these clay suspensions destabilizes the nematic phase with respect to the isotropic (disordered) phase. The polymers that we used (poly(ethylene oxide) and dextran) were too small to adopt particle-bridging conformations and small-angle X-ray scattering experiments showed that the structure of the nematic phase is not altered by polymer doping. However, the adsorption isotherm shows that the macromolecules adsorb onto the clay nanosheets, effectively coating them with a polymer layer. Our extension of Onsager's theory for polymer-coated platelets properly captures the experimental phase diagram and shows how the nematic phase destabilization can be due to the polymer adsorbing more on the platelet faces than at the rim. Because the flow properties of the nematic phase are very different from those of the isotropic phase, the presence or absence of the former phase is an important factor to be determined and considered to explain the rheological behavior of these complex systems.