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Background and Hypothesis Although the thalamus has a central role in schizophrenia pathophysiology, contributing to sensory, cognitive, and sleep alterations, the nature and dynamics of the alterations occurring within this structure remain largely elusive. Using a multimodal magnetic resonance imaging (MRI) approach, we examined whether anomalies: (1) differ across thalamic subregions/nuclei, (2) are already present in the early phase of psychosis (EP), and (3) worsen in chronic schizophrenia (SCHZ). Study Design T1-weighted and diffusion-weighted images were analyzed to estimate gray matter concentration (GMC) and microstructural parameters obtained from the spherical mean technique (intra-neurite volume fraction [VFINTRA)], intra-neurite diffusivity [DIFFINTRA], extra-neurite mean diffusivity [MDEXTRA], extra-neurite transversal diffusivity [TDEXTRA]) within 7 thalamic subregions. Results Compared to age-matched controls, the thalamus of EP patients displays previously unreported widespread microstructural alterations (VFINTRA decrease, TDEXTRA increase) that are associated with similar alterations in the whole brain white matter, suggesting altered integrity of white matter fiber tracts in the thalamus. In both patient groups, we also observed more localized and heterogenous changes (either GMC decrease, MDEXTRA increase, or DIFFINTRA decrease) in mediodorsal, posterior, and ventral anterior parts of the thalamus in both patient groups, suggesting that the nature of the alterations varies across subregions. GMC and DIFFINTRA in the whole thalamus correlate with global functioning, while DIFFINTRA in the subregion encompassing the medial pulvinar is significantly associated with negative symptoms in SCHZ. Conclusion Our data reveals both widespread and more localized thalamic anomalies that are already present in the early phase of psychosis.

The operational costs of wastewater treatment plants (WWTPs) are mainly driven by electric power consumption, making the energy-efficient operation an all-time present target for engineers and operators. A well known approach to reduce the demand for purchased electricity is the operation of an anaerobic sludge stabilisation process. Although anaerobic digesters make it possible to recover large quantities of energy-rich methane gas, additional strategies are required to handle the increased internal return flow of nitrogen, which arises with the sludge dewatering effluent (SDE). SDE treatment increases the oxygen demand and in turn the energy required for aeration. In this study, different SDE treatment processes were compared with regard to the treatment in mainstream, sidestream nitritation, as well as nitritation combined with anammox for two-stage and single-stage WWTPs. Although SDE treatment in sidestream nitritation was found to have no effect on the energy demand of single-stage WWTPs, this concept allows the treatment capacity in the activated sludge tank to be raised, while contributing to a high nitrogen removal under carbon limitation. In contrast, SDE sidestream treatment showed great potential for saving energy at two-stage WWTPs, whereby sidestream nitritation and the further treatment in the first stage was found to be the most efficient concept, with a savings of approx. 11% of the aeration energy.

Background: A pace and ablate strategy may be performed in refractory atrial fibrillation with rapid ventricular response. Objective: We aimed to assess sex-related differences in patient selection and clinical outcomes after pace and ablate. Methods: In a retrospective multicentre study, patients undergoing AV junction ablation were studied. Sex-related differences in baseline characteristics, all-cause mortality, heart failure (HF) hospitalizations, and device-related complications were assessed. Results: Overall, 513 patients underwent AV junction ablation (median age 75 years, 50% men). At baseline, men were younger (72 vs. 78 years, p < 0.001), more frequently had non-paroxysmal AF (82% vs. 72%, p = 0.006), had a lower LVEF (35% vs. 55%, p < 0.001) and more frequently had cardiac resynchronization therapy (75% vs. 25%, p < 0.001). Interventional complications were rare in both groups (1.2% vs. 1.6%, p = 0.72). Patients were followed for a median of 42 months in survivors (IQR 22–62). After 4 years of follow-up, the combined endpoint of all-cause death or HF hospitalization occurred more often in men (38% vs. 27%, p = 0.008). The same was observed for HF hospitalizations (22% vs. 11%, p = 0.021) and all-cause death (28% vs. 21%, p = 0.017). Sex category remained an independent predictor of death or HF hospitalization after adjustment for age, LVEF and type of stimulation. Lead-related complications, infections, and upgrade to ICD or CRT occurred in 2.1%, 0.2% and 3.5% of patients, respectively. Conclusions: Pace and ablate is safe with a need for subsequent device-related re-interventions in 5.8% over 4 years. We found significant sex-related differences in patient selection, and women had a more favourable clinical course after AV junction ablation.

The unexpectedly challenging synthesis of 4-pyridyl-extended dithieno[3,2-b:2',3'-d]phospholes via Stille cross-coupling is reported. The optical and electrochemical properties of the phosphoryl-bridged species were studied experimentally and computationally, and their properties were compared with those of their non-P-bridged congeners. The 4-pyridyl-extended dithienophospholes display quantitative luminescence quantum yields in solution and reversible reduction features upon methylation of the pyridine rings. Because of their very high brightness, even in water, 4-pyridyl-extended dithienophospholes are highly promising candidates for new fluorescent probes.

Despite an historical connection between the arts and sciences, in the past century, the two disciplines have been greatly siloed. However, there is a renewed interest in collaboration across the arts and sciences to support conservation practice by understanding and communicating complex environmental, social, and cultural challenges in novel ways. 6&6 was created as a transdisciplinary art–science initiative to promote a deeper appreciation of the Sonoran Desert. Six artists and six scientists were paired to create work that explored conservation issues in the Sonoran Desert and the Gulf of California. In-depth interviews were conducted with the artists and scientists throughout the 4-year initiative to understand the impact of 6&6 on their personal and professional behaviors and outlook. The findings from this case study reveal the role that intensive, place-based, and transdisciplinary art–science programs can play in shaping narratives to better communicate the patterns and processes of nature and human–environment interactions.

Despite the prominence of rare-earth complexes to act as Lewis acid catalysts in organic synthesis, the comprehensive measure of the Lewis acid strength of such compounds has yet to be performed due to incompatibilities with existing methods. We report our results in measurement of a sequence of lanthanide triflates via our recently established fluorescent Lewis adduct (FLA) method. The persistence in solution of these Lewis acids as solvated coordination complexes is accurately measurable by the FLA method. However, several of the rare-earth species exhibit fluorescence quenching, which may potentially inhibit the measurement. Nevertheless, meaningful FLA measurements were still possible, and the results correspond to both periodic trends and were even consistent with previous correlated reported data.

People receive daily environmental warnings about the risk of reaching critical climate tipping points leading to irreversible consequences. However, little is known about whether such warnings promote behavioral change, or how emotions underlie such responses. Here, we present two preregistered online experiments, in which group members can harvest financial resources from a common pool while risking collective over-exploitation causing an actual environmental externality. We find that warnings are effective and that the self-conscious emotion guilt consistently correlates with (Study 1) and mediates (Study 2) the effect of warnings on sustainable behavioral change. This suggest that warnings, as a lever of experienced guilt, may qualify as an effective strategy to promote cooperation in the climate commons.

Development of novel organics that exhibit multiple and stable redox states, limited solubility and improved conductivity is a highly rewarding direction for improving the performance of lithium-ion batteries (LIBs). As biologically derived organic molecules, carbonylpyridinium compounds have desirable and tunable redox properties, making them suitable candidates for battery applications. In this work, we report a structural evolution of carbonylpyridinium-based redox-active organics, from 2-electron accepting BMP to 4-electron accepting small, conjugated molecules (1, 2), and then to the corresponding conjugated polymers (CP1, CP2). Through suppression of dissolution and increasing electrochemical conductivity, the LIBs performance can be gradually enhanced. At a relatively high current of 0.5 A g-1, high specific capacities for 1 (100 mAh g-1), 2 (260 mAh g-1), CP1 (360 mAh g-1) and CP2 (540 mAh g-1) can be reached after 240 cycles. Particularly, the rate performance and cycling stability of CP2 surpasses many reported commercial inorganic and organic electrode materials. This work provides a promising new carbonylpyridinium-based building block featured with multiple redox centers, on the way to high performance Li-organic batteries.

Redox-active polymers have recently become promising candidates for next-generation electrode materials in lithium-ion batteries. Materials made from small molecules with one or multiple reversible redox states are required to develop high energy density organic electrodes. Here, we focus our attention on 2,1,3-benzothiadiazole (BTZ), a widely employed organic electron acceptor with a suitable redox potential (−1.48 V vs Ag/Ag+ in acetonitrile) and a large theoretical charge-storage capacity (164.5 mAh/g). In this study, we synthesized gram quantities of poly(5-vinylbenzothiadiazole) from BTZ in three synthetic steps and employed a versatile and scalable radical polymerization protocol to make the final polymer. Lithium–organic hybrid batteries using this polymer as a cathode displayed a high specific capacity of 140 mAh/g at a charge/discharge potential of 1.70 V vs Li/Li+. This polymer showed promising performance and high stability, reaching up to 85% of the theoretical capacity and maintaining 99% cou...

Contributing to and maintaining public goods are important for a functioning society. In reality, however, we see large variations in contribution behavior. While some individuals are not cooperative, others are highly so. Still others cooperate only to the extent they believe others will. Although these distinct behavioral types clearly have a divergent social impact, the sources of heterogeneity are poorly understood. We used source‐localized resting electroencephalography in combination with a model‐free clustering approach to participants' behavior in the Public Goods Game to explain heterogeneity. Findings revealed that compared to noncooperators, both conditional cooperators and unconditional cooperators are characterized by higher baseline activation in the right temporo‐parietal junction, an area involved in social cognition. Interestingly, conditional cooperators were further characterized by higher baseline activation in the left lateral prefrontal cortex, an area involved in behavioral control. Our findings suggest that conditional cooperators' better capacities for behavioral control enable them to control their propensity to cooperate and thus to minimize the risk of exploitation by noncooperators.

Summary The strength of a Lewis acid is an important parameter in establishing its utility for practical applications. Here, we report a universal fluorescence-based method for accurately determining the strength of a range of Lewis acids. Utilizing a fluorescent dithienophosphole oxide architecture, we are able to emulate the structural motif of the widely employed Gutmann-Beckett method. This allows us to precisely correlate the optical response to the strength of a Lewis acid. In comparison to commonly used methods that employ 31P NMR chemical shifts or quantum-chemical calculations, our method strongly suggests that using fluorescent Lewis acid-base adducts (FLAs) is more reliable. Moreover, our method provides a direct measure of the Lewis acidity of a given solution, independent of the Lewis base, with direct implications to the overall utility of a Lewis acid in practical applications.

Given the urgency of climate change mitigation, motivating individuals to behave in sustainable ways constitutes a key challenge for environmental science. Although many studies evidence people’s long-lasting pro-environmental attitudes, such attitudes often do not translate into behavior. The present research hypothesizes that cognitive resources are a crucial moderator, explaining when pro-environmental attitudes turn into behavior. Specifically, we investigate the attitude–behavior gap while taking a “cognition perspective” on environmental behavior. Using experience sampling, the present research demonstrates that individual differences in central aspects of cognitive control (assessed by working memory capacity) moderate the relationship between environmental attitudes and behavior. Our correlational findings suggest that people with positive environmental attitudes also require high working memory capacity to behave in line with their ideals. Our results do not only provide empirical support for recent theorizing in environmental research, but, perhaps more importantly, might offer a central lever for behavioral change initiatives (e.g., “nudging”).

Over the years, various multiparameter methods have been developed to measure the strength of a Lewis acid. However, a major challenge for these measurements lies in the complexity that arises from variables such as solvent and other fundamental interactions, as well as perturbations of Lewis acids as their reaction environment changes. Herein, we evaluate the impact of solvent effects on the Fluorescent Lewis Adduct (FLA) method using a series of representative Lewis acids. The solution-state nature of the FLA method in particular, offers the ability to correlate Lewis Acid Units (LAUs) obtained from the FLA measurement with chemical reactivity. The binding of a Lewis acid in various solvents reveals a measurable dichotomy between both polarity and donor ability of the solvent. While not strictly separable, we observe that, as solvent polarity increases observed LAUs increase; however, as solvent donor ability increases, the observed LAUs decrease. This dichotomy was confirmed by titration data and catalytic Diels-Alder cycloaddition and hydrosilylation reactions, illustrating that solvation effects can be appropriately gauged by LAU values determined from the FLA method.

The use of donor–π–acceptor (D–π–A) skeletons is an effective strategy for the design of fluorophores with red-shifted emission. In particular, the use of amino and boryl moieties as the electron-donating and -accepting groups, respectively, can produce dyes that exhibit high fluorescence and solvatochromism. Herein, we introduce a dithienophosphole P-oxide scaffold as an acceptor–spacer to produce a boryl- and amino-substituted donor–acceptor–acceptor (D–A–A) π-system. The thus obtained fluorophores exhibit emission in the near-infrared (NIR) region, while maintaining high fluorescence quantum yields even in polar solvents (e.g. λem = 704 nm and ΦF = 0.69 in CH3CN). A comparison of these compounds with their formyl- or cyano-substituted counterparts demonstrated the importance of the boryl group for generating intense emission. The differences among these electron-accepting substituents were examined in detail using theoretical calculations, which revealed the crucial role of the boryl group in lowering the nonradiative decay rate constant by decreasing the non-adiabatic coupling in the internal conversion process. The D–A–A framework was further fine-tuned to improve the photostability. One of these D–A–A dyes was successfully used in bioimaging to visualize the blood vessels of Japanese medaka larvae and mouse brain., Combination of electron-accepting diarylboryl terminal groups and dithienophosphole oxide spacers with electron-donating triarylamine moieties produces donor–acceptor–acceptor type π-systems, which exhibit emissions in the near-infrared region.

The unexpectedly challenging synthesis of 4-pyridyl-extended dithieno[3,2

The evaluation of the chromaticity of a series of fluorescent Lewis adducts with highly luminescent dithienophospholes enables the unequivocal determination of the strength of Lewis acids. Our method provides a simple, robust, and efficient avenue to discern an exhaustive list of species from across the period table.

Low molecular weight organic molecules that can accept multiple electrons at high reduction potentials are sought after as electrode materials for high-energy sustainable batteries. To date their synthesis has been difficult, and organic scaffolds for electron donors significantly outnumber electron acceptors. Herein, we report the synthesis and electronic properties of two highly electron-deficient phosphaviologen derivatives from a phosphorus-bridged 4,4'-bipyridine and characterize their electrochemical properties. Phosphaviologen sulfide (PVS) and P-methyl phosphaviologen (PVM) accept two and three electrons at high reduction potentials, respectively. PVM can reversibly accept three electrons between 3–3.6 V vs. Li/Li+ with an equivalent molecular weight of 102 g (mol−1 e−) (262 mA h g−1), making it a promising scaffold for sustainable organic electrode materials having high specific energy densities., Two strongly electron-accepting viologens, including an intriguing tricationic species, are reported. The utility of the tricationic viologen for energy storage has been showcased via use as electrode in a proof-of-concept battery.

Why are some people more biased than others in their implicit evaluations during social interaction? The dispositional determinants of individual differences in implicit intergroup bias are poorly understood. Here, we explored whether such variability might be explained by stable neural traits. For that purpose, we used the source-localized resting electroencephalograms of 83 members of naturalistic social groups to explain their bias in an in-/outgroup implicit association test. Lower levels of resting theta current density in the right temporo-parietal junction (TPJ) were associated with stronger implicit intergroup bias and explained unique variability in bias beyond relevant personality questionnaires. These findings demonstrate the added value of the neural trait approach in predicting inter-individual differences in implicit social cognition. Given that low levels of resting theta current density during wakefulness likely reflect increased cortical activation, our results suggest that individuals with an efficiently working right TPJ possess capacities to mediate specific cognitive processes that predispose them towards stronger implicit intergroup bias. As the human species has evolved living in distinct social groups, the capacity to quickly differentiate friend from foe became highly adaptive and might thus constitute an essential part of human nature.

Summary The synthesis of a π-conjugated organophosphorus species with bridging P–P unit is reported. Because of the pyramidal geometry of the phosphorus centers, the molecular scaffold provides intriguing electronic communication throughout the three-dimensional structure via π-σ-π conjugation in stepwise fashion. The dimeric species was serendipitously found to be accessible via a reaction of the corresponding P-amino-phosphole precursor through mediation with the hard Lewis acid BF3. We provide detailed mechanistic studies toward a suitable reaction mechanism that was also verified via computational means. Moreover, we elaborate the utility of the biphosphole via phosphorus functionalization that lends further proof for the step conjugation provided by the unique phosphorus-based molecular architecture.

When people sense that another person tries to control their decisions, some people will act against the control, whereas others will not. This individual tendency to control‐averse behavior can have far‐reaching consequences, such as engagement in illegal activities or noncompliance with medical treatments. Although individual differences in control‐averse behavior have been well documented in behavioral studies, their neurological basis is less well understood. Here, we use a neural trait approach to examine whether individual differences in control‐averse behavior might be linked to stable brain‐based characteristics. To do so, we analyze the association between intrinsic connectivity networks as measured by resting state functional magnetic resonance imaging and control‐averse behavior in an economic exchange game. In this game, subjects make choices that are either free or controlled by another person, with real consequences to both interaction partners. We find that the individual level of control‐averse behavior can be positively predicted by intrinsic connectivity within the salience network, but not the central executive network or the default mode network. Specifically, subjects with a more prominent connectivity hub in the dorsal anterior cingulate cortex show greater levels of control‐averse behavior. This finding provides the first evidence that the heterogeneity in control‐averse behavior might originate in systematic differences of the stable functional brain organization.

Fairness norm compliance is critical in any society. However, norm compliant behavior is very heterogeneous. Some people are reliably fair (voluntary compliers). Some are fair to avoid sanctions (sanction-based compliers), and some are reliably unfair (non-compliers). These types play divergent roles in society. However, they remain poorly understood. Here, we combined neural measures (resting electroencephalography and event-related potentials) and economic paradigms to better understand these types. We found that voluntary compliers are characterized by higher baseline activation in the right temporo-parietal junction, suggesting better social cognition capacity compared to sanction-based compliers and non-compliers. The latter two types are differentiated by (a) baseline activation in the dorso-lateral prefrontal cortex, a brain area known to be involved in self-control processes, and (b) event-related potentials in a classic self-control task. Both results suggest that sanction-based compliers have better self-control capacity than non-compliers. These findings improve our understanding of fairness norm compliance. Broadly, our findings suggest that established training techniques that boost self-control might help non-compliers adhere to fairness norms.

The P-functionalization of dithieno[3,2-b:2′,3′-d]phosphole oxides via reaction of a P-chloro derivative with aromatic amines and alcohols is reported. The reactions proceed rapidly and provide the products in good yields, highlighting the synthetic versatility of the P-chloro dithienophosphole oxide toward effectively modifying the molecular scaffold without the need for elaborate phosphorus precursor syntheses. The resulting phosphinic amide and ester products show interesting photophysics that strongly depend on the nature of the P-substituent such as high luminescence quantum yields for the ester derivatives, as well as aggregation-induced enhanced emission for the amide derivative. The phosphinic amide species also shows intriguing self-assembly in the solid state via hydrogen bonding.