Elements of exogenous attentional cueing preserved during optokinetic motion of the visual scene.

Navigating through our environment raises challenges for perception by generating salient background visual motion and eliciting prominent eye movements to stabilise the retinal image. It remains unclear if exogenous spatial attentional orienting is possible during background motion and the eye movements it causes and whether this compromises the underlying neural processing. To test this, we combined exogenous orienting, visual scene motion, and electroencephalography (EEG). A total of 26 participants viewed a background of moving black and grey bars (optokinetic stimulation). We tested for effects of non-spatially predictive peripheral cueing on visual motion discrimination of a target dot, presented either at the same (valid) or opposite (invalid) location as the preceding cue. Valid cueing decreased reaction times not only when participants kept their gaze fixed on a central point (fixation blocks) but also even when there was no fixation point, so that participants performed intensive, repetitive tracking eye movements (eye movement blocks). Overall, manual response reaction times were slower during eye movements. Cueing also produced reliable effects on neural activity on either block, including within the first 120 ms of neural processing of the target. The key pattern with larger event-related potential (ERP) amplitudes on invalid versus valid trials showed that the neural substrate of exogenous cueing was highly similar during eye movements or fixation. Exogenous peripheral cueing and its neural correlates are robust against distraction from the moving visual scene, important for perceptual cognition during navigation.

Biodiversity in and around Greenhouses: Benefits and Potential Risks for Pest Management.

One of the ecosystem services of biodiversity is the contribution to pest control through conservation and stimulation of natural enemies. However, whether plant diversity around greenhouses is beneficial or a potential risk is heavily debated. In this review, we argue that most greenhouse pests in temperate climates are of exotic origin and infest greenhouses mainly through transportation of plant material. For indigenous pests, we discuss the potential ways in which plant diversity around greenhouses can facilitate or prevent pest migrations into greenhouses. As shown in several studies, an important benefit of increased plant diversity around greenhouses is the stimulation of indigenous natural enemies that migrate to greenhouses, where they suppress both indigenous and exotic pests. How this influx can be supported by specific plant communities, plant characteristics, and habitats while minimising risks of increasing greenhouse pest densities, virus transmission, or hyperparasitism needs further studies. It also requires a better understanding of the underlying processes that link biodiversity with pest management. Inside greenhouses, plant biodiversity can also support biological control. We summarise general methods that growers can use to enhance pest control with functional biodiversity and suggest that it is particularly important to study how biodiversity inside and outside greenhouses can be linked to enhancement of biological pest control with both released and naturally occurring species of natural enemies.

The influence of TMS of the rTPJ on attentional control and mentalizing.

Mentalizing is the powerful cognitive ability to understand others. By attributing mental states to others, we become able to explain and predict their behavior. The right temporoparietal junction (rTPJ) plays a key role in processing models of mental states. Yet, a different line of research suggests that the rTPJ is crucially involved in attentional control, prompting debates on its cognitive function. In this pre-registered neuro-navigated event-related TMS study, we tested for the rTPJ's specificity in mentalizing and attentional control. We interfered with its activity in a recently developed spatial cueing paradigm in which another's mental states were apparently task-relevant, allowing direct comparison of TMS effects on attention and mentalizing. We contrasted effects with a nearby control TMS site. Our confirmatory analysis showed no evidence for an involvement of the rTPJ in mentalizing or attentional control, presumably due to an observed large inter-individual variability of TMS effects on context and validity. To follow up this finding, we conducted exploratory analyses which revealed that rTPJ TMS had an influence on both attentional control and mentalizing. TMS effects on attention and mentalizing co-varied across participants: participants responding most to rTPJ TMS on mentalizing were also those for whom rTPJ TMS increased the attentional effect the most. This provides further evidence against total absolute segregation between mentalizing and attention within the rTPJ. Rather, our results suggest a common cognitive mechanism in both domains for which the rTPJ is necessary, paving the way for future research to cross-validate and extend these findings.

V5/MT+ modulates spatio-temporal integration differently across and within hemifields: Causal evidence from TMS.

It is unclear how the brain reaches the correct balance between temporal and spatial processing necessary to perceive motion across space. Here, we tested whether visual motion area V5/MT + plays a causal role in Ternus illusion. Ternus displays can be perceived as showing either group motion or element motion and are empirically useful for dissociating temporal and spatial grouping across visual fields. Online single-pulse TMS was applied to observers during the presentation of Ternus displays, either within or across hemifields, over left V5/MT + or, respectively, a control site in the left somatosensory cortex, or an additional 'Sham' control condition. In the cross-hemifields condition, observers perceived more element motion with TMS over left V5/MT + than in either control condition. By contrast, in the within-hemifield condition, observers reported more group motion after left V5/MT + TMS. Our findings demonstrate a causal role of left V5/MT+ in the spatio-temporal grouping of Ternus apparent motion, and in maintaining the balance of spatio-temporal processing both within and across individual hemifields.

Wide-Bite-Angle Diphosphine Ligands in Thermally Activated Delayed Fluorescent Copper(I) Complexes: Impact on the Performance of Electroluminescence Applications.

We report a series of seven cationic heteroleptic copper(I) complexes of the form [Cu(P^P)(dmphen)]BF4, where dmphen is 2,9-dimethyl-1,10-phenanthroline and P^P is a diphosphine chelate, in which the effect of the bite angle of the diphosphine ligand on the photophysical properties of the complexes was studied. Several of the complexes exhibit moderately high photoluminescence quantum yields in the solid state, with ΦPL of up to 35%, and in solution, with ΦPL of up to 98%. We were able to correlate the powder photoluminescence quantum yields with the % Vbur of the P^P ligand. The most emissive complexes were used to fabricate both organic light-emitting diodes and light-emitting electrochemical cells (LECs), both of which showed moderate performance. Compared to the benchmark copper(I)-based LECs, [Cu(dnbp)(DPEPhos)]+ (maximum external quantum efficiency, EQEmax = 16%), complex 3 (EQEmax = 1.85%) showed a much longer device lifetime (t1/2 = 1.25 h and >16.5 h for [Cu(dnbp)(DPEPhos)]+ and complex 3, respectively). The electrochemiluminescence (ECL) properties of several complexes were also studied, which, to the best of our knowledge, constitutes the first ECL study for heteroleptic copper(I) complexes. Notably, complexes exhibiting more reversible electrochemistry were associated with higher annihilation ECL as well as better performance in a LEC.

Self-initiation Inhibits the Postural and Electrophysiological Responses to Optic Flow and Button Pressing.

As we move through our environment, our visual system is presented with optic flow, a potentially important cue for perception, navigation and postural control. How does the brain anticipate the optic flow that arises as a consequence of our own movement? Converging evidence suggests that stimuli are processed differently by the brain if occurring as a consequence of self-initiated actions, compared to when externally generated. However, this has mainly been demonstrated with auditory stimuli. It is not clear how this occurs with optic flow. We measured behavioural, neurophysiological and head motion responses of 29 healthy participants to radially expanding, vection-inducing optic flow stimuli, simulating forward transitional motion, which were either initiated by the participant's own button-press ("self-initiated flow") or by the computer ("passive flow"). Self-initiation led to a prominent and left-lateralized inhibition of the flow-evoked posterior event-related alpha desynchronization (ERD), and a stabilisation of postural responses. Neither effect was present in control button-press-only trials, without optic flow. Additionally, self-initiation also produced a large event-related potential (ERP) negativity between 130-170 ms after optic flow onset. Furthermore, participants' visual induced motion sickness (VIMS) and vection intensity ratings correlated positively across the group - although many participants felt vection in the absence of any VIMS, none reported the opposite combination. Finally, we found that the simple act of making a button press leads to a detectable head movement even when using a chin rest. Taken together, our results indicate that the visual system is capable of predicting optic flow when self-initiated, to affect behaviour.

Depolymerization of biorefinery lignin by improved laccases of the white-rot fungus Obba rivulosa.

Fungal laccases are attracting enzymes for sustainable valorization of biorefinery lignins. To improve the lignin oxidation capacity of two previously characterized laccase isoenzymes from the white-rot fungus Obba rivulosa, we mutated their substrate-binding site at T1. As a result, the pH optimum of the recombinantly produced laccase variant rOrLcc2-D206N shifted by three units towards neutral pH. O. rivulosa laccase variants with redox mediators oxidized both the dimeric lignin model compound and biorefinery poplar lignin. Significant structural changes, such as selective benzylic α-oxidation, were detected by nuclear magnetic resonance analysis, although no polymerization of lignin was observed by gel permeation chromatography. This suggests that especially rOrLcc2-D206N is a promising candidate for lignin-related applications.

Multi-nuclear, high-pressure, operando FlowNMR spectroscopic study of Rh/PPh3 - catalysed hydroformylation of 1-hexene.

The hydroformylation of 1-hexene with 12 bar of 1 : 1 H2/CO in the presence of the catalytic system [Rh(acac)(CO)2]/PPh3 was successfully studied by real-time multinuclear high-resolution FlowNMR spectroscopy at 50 °C. Quantitative reaction progress curves that yield rates as well as chemo- and regioselectivities have been obtained with varying P/Rh loadings. Dissolved H2 can be monitored in solution to ensure true operando conditions without gas limitation. 31P{1H} and selective excitation 1H pulse sequences have been periodically interleaved with 1H FlowNMR measurements to detect Rh-phosphine intermediates during the catalysis. Stopped-flow experiments in combination with diffusion measurements and 2D heteronuclear correlation experiments showed the known tris-phosphine complex [RhH(CO)(PPh3)3] to generate rapidly exchanging isomers of the bis-phosphine complex [Rh(CO)2(PPh3)2] under CO pressure that directly enter the catalytic cycle. A new mono-phosphine acyl complex has been identified as an in-cycle reaction intermediate.

Pesticides do not significantly reduce arthropod pest densities in the presence of natural enemies.

Chemical pesticides remain the main agents for control of arthropod crop pests despite increased concern for their side effects. Although chemical pesticide applications generally result in short-term decreases of pest densities, densities can subsequently resurge to higher levels than before. Thus, pesticide effects on pest densities beyond a single pest generation may vary, but they have not been reviewed in a systematic manner. Using mathematical predator-prey models, we show that pest resurgence is expected when effective natural enemies are present, even when they are less sensitive to pesticides than the pest. Model simulations over multiple pest generations predict that pest resurgence due to pesticide applications will increase average pest densities throughout a growing season when effective natural enemies are present. We tested this prediction with a meta-analysis of published data of field experiments that compared effects of chemical control of arthropod plant pests in the presence and absence of natural enemies. This largely confirmed our prediction: overall, pesticide applications did not reduce pest densities significantly when natural enemies were present, which concerned the vast majority of cases. We also show that long-term pesticide effectiveness is underreported and suggest that pest control by natural enemies deserves more attention.

Reducing variability of perceptual decision making with offline theta-burst TMS of dorsal medial frontal cortex.

BACKGROUND: Recent evidence suggests that the dorsal medial frontal cortex (dMFC) may make an important contribution to perceptual decision-making, and not only to motor control. OBJECTIVE/HYPOTHESIS: By fitting psychometric functions to behavioural data after TMS we tested whether the dMFC is critical specifically for the precision and/or bias of perceptual judgements. Additionally we aimed to disentangle potential roles of the dMFC in dealing with perceptual versus response switching. METHODS: A subjective visual vertical task (SVV) was used in which participants weight visual (and other, e.g., vestibular) information to establish whether a line is oriented vertically. To ensure a high perceptual demand (putatively necessary to demonstrate a dMFC involvement) SVV lines were presented inside pop-out targets within a visual search array. Distinct features of perceptual performance were analysed before as compared to following theta-burst TMS stimulation of the dMFC, a control site, or no stimulation, in three groups, each of 20 healthy participants. RESULTS: dMFC stimulation improved the precision of verticality judgments. Moreover, dMFC stimulation improved accuracy, selectively when response switches occurred with perceptual repeats. CONCLUSION: These findings point to a causal role of the dMFC in establishing the precision of perceptual decision making, demonstrably dissociable from an additional role in motor control in attentionally demanding contexts.

Copper-Catalyzed Carbonylative Hydroamidation of Styrenes to Branched Amides.

Amides are one of the most ubiquitous functional groups in synthetic and medicinal chemistry. Novel and rapid synthesis of amides remains in high demand. In this communication, a general and efficient procedure for branch-selective hydroamidation of vinylarenes with hydroxyamine derivatives enabled by copper catalysis has been developed for the first time. The reaction proceeds under mild conditions and tolerates a broad range of functional groups. Applying a chiral phosphine ligand, an enantioselective variant of this transformation was achieved, affording a variety of chiral α-amides with excellent enantioselectivities (up to 99 % ee) and high yields.

P-Chirogenic Diphosphazanes with Axially Chiral Substituents and Their Use in Rh-Catalyzed Asymmetric Hydrogenation.

A convenient synthesis of enantiopure P-chirogenic diphosphazanes incorporating bulky bisphenol and 1,1'-bi-2-naphthol-derived substituents via the functionalization of a readily accessible enantiopure lithium phosphinoamide with chlorophosphoridites was developed. Since the product requires no subsequent deprotection, the protocol provides an easy, convenient synthesis of P-chirogenic ligands on the gram scale. The ligands were applied in the Rh-catalyzed asymmetric hydrogenation of benchmark substrates furnishing enantiomeric excess values up to 96%.

Catalytic reductive aminations using molecular hydrogen for synthesis of different kinds of amines.

Reductive aminations constitute an important class of reactions widely applied in research laboratories and industries for the synthesis of amines as well as pharmaceuticals, agrochemicals and biomolecules. In particular, catalytic reductive aminations using molecular hydrogen are highly valued and essential for the cost-effective and sustainable production of different kinds of amines and their functionalization. These reactions couple easily accessible carbonyl compounds (aldehydes or ketones) with ammonia, amines or nitro compounds in the presence of suitable catalysts and hydrogen that enable the preparation of linear and branched primary, secondary and tertiary amines including N-methylamines and molecules used in life science applications. In general, amines represent valuable fine and bulk chemicals, which serve as key precursors and central intermediates for the synthesis of advanced chemicals, life science molecules, dyes and polymers. Noteworthily, amine functionalities are present in a large number of pharmaceuticals, agrochemicals and biomolecules, and play vital roles in the function of these active compounds. In general, reductive aminations are challenging processes, especially for the syntheses of primary amines, which often are non-selective and suffer from over-alkylation and reduction of carbonyl compounds to the corresponding alcohols. Hence, the development of suitable catalysts to perform these reactions in a highly efficient and selective manner is crucial and continues to be important and attracts scientific interest. In this regard, both homogeneous and heterogeneous catalysts have successfully been developed for these reactions to access various amines. There is a need for a comprehensive review on catalytic reductive aminations to discuss the potential catalysts used and applicability of this methodology in the preparation of different kinds of amines, which are of commercial, industrial and medicinal importance. Consequently, in this review we discuss catalytic reductive aminations using molecular hydrogen and their applications in the synthesis of functionalized and structurally diverse benzylic, heterocyclic and aliphatic primary, secondary and tertiary amines as well as N-methylamines and more complex drug targets. In addition, mechanisms of reductive aminations including selective formation of desired amine products as well as possible side reactions are emphasized. This review aims at the scientific communities working in the fields of organic synthesis, catalysis, and medicinal and biological chemistry.

An Introduction to Model Compounds of Lignin Linking Motifs; Synthesis and Selection Considerations for Reactivity Studies.

The development of fundamentally new valorization strategies for lignin plays a vital role in unlocking the true potential of lignocellulosic biomass as sustainable and economically compatible renewable carbon feedstock. In particular, new catalytic modification and depolymerization strategies are required. Progress in this field, past and future, relies for a large part on the application of synthetic model compounds that reduce the complexity of working with the lignin biopolymer. This aids the development of catalytic methodologies and in-depth mechanistic studies and guides structural characterization studies in the lignin field. However, due to the volume of literature and the piecemeal publication of methodology, the choice of suitable lignin model compounds is far from straight forward, especially for those outside the field and lacking a background in organic synthesis. For example, in catalytic depolymerization studies, a balance between synthetic effort and fidelity compared to the actual lignin of interest needs to be found. In this Review, we provide a broad overview of the model compounds available to study the chemistry of the main native linking motifs typically found in lignins from woody biomass, the synthetic routes and effort required to access them, and discuss to what extent these represent actual lignin structures. This overview can aid researchers in their selection of the most suitable lignin model systems for the development of emerging lignin modification and depolymerization technologies, maximizing their chances of successfully developing novel lignin valorization strategies.

Copper-Catalyzed Regioselective Borocarbonylative Coupling of Unactivated Alkenes with Alkyl Halides: Synthesis of ß-Boryl Ketones.

The borocarbonylative coupling of unactivated alkenes with alkyl halides remains a challenge. In this communication, a Cu-catalyzed borocarbonylative coupling of unactivated alkenes with alkyl halides for the synthesis of ß-boryl ketones has been developed. A broad range of ß-boryl ketone derivatives was prepared in moderate to excellent yields with complete regioselectivity.

Ultra-small cobalt nanoparticles from molecularly-defined Co-salen complexes for catalytic synthesis of amines.

We report the synthesis of in situ generated cobalt nanoparticles from molecularly defined complexes as efficient and selective catalysts for reductive amination reactions. In the presence of ammonia and hydrogen, cobalt-salen complexes such as cobalt(ii)-N,N'-bis(salicylidene)-1,2-phenylenediamine produce ultra-small (2-4 nm) cobalt-nanoparticles embedded in a carbon-nitrogen framework. The resulting materials constitute stable, reusable and magnetically separable catalysts, which enable the synthesis of linear and branched benzylic, heterocyclic and aliphatic primary amines from carbonyl compounds and ammonia. The isolated nanoparticles also represent excellent catalysts for the synthesis of primary, secondary as well as tertiary amines including biologically relevant N-methyl amines.

Shift in lateralization during illusory self-motion: EEG responses to visual flicker at 10 Hz and frequency-specific modulation by tACS.

Self-motion perception is a key aspect of higher vestibular processing, suggested to rely upon hemispheric lateralization and alpha-band oscillations. The first aim of this study was to test for any lateralization in the EEG alpha band during the illusory sense of self-movement (vection) induced by large optic flow stimuli. Visual stimuli flickered at alpha frequency (approx. 10 Hz) in order to produce steady state visually evoked potentials (SSVEPs), a robust EEG measure which allows probing the frequency-specific response of the cortex. The first main result was that differential lateralization of the alpha SSVEP response was found during vection compared with a matched random motion control condition, supporting the idea of lateralization of visual-vestibular function. Additionally, this effect was frequency-specific, not evident with lower frequency SSVEPs. The second aim of this study was to test for a causal role of the right hemisphere in producing this lateralization effect and to explore the possibility of selectively modulating the SSVEP response. Transcranial alternating current stimulation (tACS) was applied over the right hemisphere simultaneously with SSVEP recording, using a novel artefact removal strategy for combined tACS-EEG. The second main result was that tACS enhanced SSVEP amplitudes, and the effect of tACS was not confined to the right hemisphere. Subsequent control experiments showed the effect of tACS requires the flicker frequency and tACS frequency to be closely matched and tACS to be of sufficient intensity. Combined tACS-SSVEPs are a promising method for future investigation into the role of neural oscillations and for optimizing tACS.

[Mechanical bowel obstruction in geriatric patients : Etiology and perioperative morbidity/mortality compared with a younger cohort]. / Der mechanische Ileus bei geriatrischen Patienten : Ätiologie und perioperative Morbidität/Mortalität im Vergleich zu einer jüngeren Patientenkohorte.

BACKGROUND: Mechanical bowel obstruction is a common condition in geriatric patients in the emergency department. It accounts for up to 50% of all emergency surgeries in the elderly. In recent years, diagnosis and treatment of mechanical bowel obstruction has improved, but little is known whether elderly patients benefit from modern treatment approaches. OBJECTIVE: The aim of the work is to generate knowledge about possible improvement of diagnosis and treatment of mechanical bowel obstruction in the elderly. METHODS: A retrospective review of 132 patients was performed comparing geriatric (>80 years of age) and nongeriatric patients (50-70 years of age) admitted with mechanical bowel obstruction. Etiology, time from first contact to operation, bowel resection rate and morbidity/mortality were compared. Data analysis included Fisher's test and Student t­test. RESULTS: In patients under 70 years of age it took 18.23 ± 0.79 h from first contact until laparotomy in the operating room (OR) vs. 43.38 ± 12.08 h in patients above 80 years of age (p = 0.0111). In 58.9% of geriatric patients, resection of bowel was necessary, while only 35.3% of <70-year-old patients needed bowel resection (p = 0.0401). In all, 50% of geriatric patients experienced major complications (Dindo/Clavien >IIIB) vs. only 12.7% of 50- to 70-year-old patients (p = 0.0002). Postoperative stay in the intensive care unit was significantly prolonged in geriatric patients compared to younger patients (93.97 ± 17.36 h vs. 26.11 ± 3.73 h, p < 0.0001). CONCLUSIONS: Time from first contact in the emergency department until laparotomy in the OR is prolonged in geriatric patients, leading to a higher probability of bowel resection with greater morbidity and mortality. Diagnostics should be intensified and accelerated in geriatric patients. Emergency surgery should be considered earlier.

Mobile steady-state evoked potential recording: Dissociable neural effects of real-world navigation and visual stimulation.

BACKGROUND: The ability to record brain activity in humans during movement, and in real world environments, is an important step towards understanding cognition. Electroencephalography (EEG) is well suited to mobile applications but suffers from the problem of artefacts introduced into the signal during movement. Steady state visually evoked potentials (SSVEPs) give an excellent signal-to-noise ratio and averaging a sufficient number of trials will eventually remove any noise not phase locked to the visual flicker. NEW METHOD: Here we present a method for producing SSVEPs of real world environments using modified LCD shutter glasses, which are commonly used for 3D TV, by adapting the glass to flicker at neurophysiologically relevant frequencies (alpha band). Participants viewed a room whilst standing and walking. Either the left or right side of the room was illuminated, to test if it is possible to recover the resulting SSVEPs when walking, as well as to probe the effect of walking on neural activity. Additionally, by using a signal generator to produce "simulated SSVEPs" on the scalp we can demonstrate that this method is able to accurately recover evoked neural responses during walking. RESULTS: The amplitude of SSVEPs over right parietal cortex was reduced by walking. Furthermore, the waveform and phase of the SSVEPs is highly preserved between walking and standing, but was sensitive to whether the left or right side of the room was illuminated. CONCLUSIONS: This method allows probing neural responses during natural movements within real environments, potentially at a wide range of frequencies.

Right frontal eye field has perceptual and oculomotor functions during optokinetic stimulation and nystagmus.

The right frontal eye field (rFEF) is associated with visual perception and eye movements. rFEF is activated during optokinetic nystagmus (OKN), a reflex that moves the eye in response to visual motion (optokinetic stimulation, OKS). It remains unclear whether rFEF plays causal perceptual and/or oculomotor roles during OKS and OKN. To test this, participants viewed a leftward-moving visual scene of vertical bars and judged whether a flashed dot was moving. Single pulses of transcranial magnetic stimulation (TMS) were applied to rFEF on half of trials. In half of blocks, to explore oculomotor control, participants performed an OKN in response to the OKS. rFEF TMS, during OKN, made participants more accurate on trials when the dot was still, and it slowed eye movements. In separate blocks, participants fixated during OKS. This not only controlled for eye movements but also allowed the use of EEG to explore the FEF's role in visual motion discrimination. In these blocks, by contrast, leftward dot motion discrimination was impaired, associated with a disruption of the frontal-posterior balance in alpha-band oscillations. None of these effects occurred in a control site (M1) experiment. These results demonstrate multiple related yet dissociable causal roles of the right FEF during optokinetic stimulation.NEW & NOTEWORTHY This study demonstrates causal roles of the right frontal eye field (FEF) in motion discrimination and eye movement control during visual scene motion: previous work had only examined other stimuli and eye movements such as saccades. Using combined transcranial magnetic stimulation and EEG and a novel optokinetic stimulation motion-discrimination task, we find evidence for multiple related yet dissociable causal roles within the FEF: perceptual processing during optokinetic stimulation, generation of the optokinetic nystagmus, and the maintenance of alpha oscillations.