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Grapheme-colour synaesthesia is a neurological trait that causes lifelong colour associations for letter and numbers. Synaesthesia studies have demonstrated differences between synaesthetes and non-synaesthetes in ways that extend beyond synaesthesia itself (e.g., differences in their cognition, personality, and creativity). This research has focused almost exclusively on adult synaesthetes, and little is known about the profiles of synaesthetic children. By and large, findings suggest advantages for synaesthetes (e.g., Chun & Hupe, 2016; Havlik et al., 2015 , Rothen et al., 2012 ; Rouw & Scholte, 2016; Simner & Bain, 2018) although differences in mathematical ability are unclear: some research indicates advantages (e.g., Green & Goswami, 2008) whilst others suggest difficulties (e.g., Rich et al., 2005). In the current study, we tested numerical cognition in a large group of children with grapheme-colour synaesthesia. Synaesthetes with coloured numbers showed advantages over their peers in their sense of numerosity, but not in their curriculum mathematics ability. We discuss how our findings speak to models for synaesthesia, to methodologies for assessing number cognition (e.g., dot numerosity tasks), and to the wider educational practice of using coloured number-tools in schools (e.g., Numicon; Oxford University Press, 2018).

The Education (Additional Support for Learning) (Scotland) Act 2004 boosted the rights of parents of children with additional support needs (ASN) by improving access to information, instituting a Code of Practice and establishing new redress mechanisms such as the ASN Tribunal and independent mediation. More than a decade later, Scottish legislation enacted in 2016 and implemented in 2018 attempted to increase children’s rights, broadly placing them on a par with those of parents and young people. This paper draws on data from an ESRC project entitled Autonomy, Rights and Children with Special Needs: A New Paradigm? (ES/P002641/1). Analysis of Scottish Government policy and legislation, key informant interviews and official statistics are used to examine the extent to which the new rights are likely to be realised in practice, given the complexity of the legislation and competition between discourses of needs, broadly synonymous with the wellbeing agenda, and rights. The paper concludes with a discussion of the lessons which may be learnt from the Scottish experience, which will be of interest to an international audience.

International audience; This paper describes the synthesis, structure, conformation and configurational stability of novel 8-atom meta-meta’ linked biaryls, as models for controlling the ratio of atropisomers through remote central chirality. The synthesis of model compounds is described where the configuration of the linker is provided by reduced C4 and C6 sugars. Their properties have been examined by X-ray, NMR and ECD. Taken together, they provide information on the conformation of the linking chain in each case and indicate a barrier to atropisomerisation in the region of 55 kJ mol−1. For the diastereomeric C6 compounds, the preferred atropisomer is defined by the configuration of the backbone secondary methyl groups. Computational analysis confirms the direction of axial chirality from ECD spectra and offers a model for the distinction between the (R,R,R,R) and (S,R,R,S) C6-isomers..

Previous research into personality and synaesthesia has focused on adult populations and yielded mixed results. One particular challenge has been to distinguish traits associated with synaesthesia, from traits associated with the ways in which synaesthetes were recruited. In the current study we addressed recruitment issues by testing randomly sampled synaesthetes, and we looked particularly at synaesthesia in childhood. Our child synaesthetes were identified by a screening program across 22 primary schools in the South East of England (n = 3387; children aged 6 to 10 years old). This identified two types of synaesthete (grapheme-colour synaesthesia and sequence-personality synaesthesia), and we tested their personalities using both child-report and parent-report measures. We found strong support for synaesthesia being associated with high Openness to Experience, a personality trait linked to intelligence and creativity. Both synaesthesia subtypes showed this feature, supporting previous research in adults (1-3). We additionally found low Extraversion in grapheme-colour synaesthetes and high Conscientiousness in sequence-personality synaesthetes. We discuss our results with reference to earlier recruitment issues, and as to how perceptual differences such as synaesthesia might link to trait-differences in personality.

Cognitive benefits associated with grapheme-colour synaesthesia in adults are well documented, but far less is known about whether such benefits might arise in synaesthetes as children. One previous study on a very small group of randomly sampled child synaesthetes found cognitive benefits in short-term memory and processing speed (the ability to quickly scan an array of images and discriminate between them), but was inconclusive for a test of receptive vocabulary. Using a stratified population sample ( Growing Up in Scotland Project, Edinburgh, UK: Scottish Executive, 2007), we investigated the performance of a large cohort of child grapheme-colour synaesthetes using four literacy measures taken at age 10 years. These were three verbal comprehension measures (expressive vocabulary, receptive vocabulary and sentence comprehension) and one measure of academic self-concept in reading (plus one measure of academic self-concept in numeracy as a comparison). After controlling for demographic differences between groups, synaesthetes showed significantly enhanced performance for expressive and receptive vocabulary compared to their peers, but no benefits in sentence comprehension. Child synaesthetes also reported significantly higher academic self-concept for reading, but not for numeracy. Finally, we found that synaesthetes made significantly more progress than controls across the primary school years, although they began school with no a priori advantage. Our study provides powerful new evidence that children with grapheme-colour synaesthesia show vocabulary and literacy differences, which we contextualize within a theory of synaesthetic development. This article is part of a discussion meeting issue ‘Bridging senses: novel insights from synaesthesia’.

Synaesthesia is a neurological phenomenon affecting perception, where triggering stimuli (e.g. letters and numbers) elicit unusual secondary sensory experiences (e.g. colours). Family-based studies point to a role for genetic factors in the development of this trait. However, the contributions of common genomic variation to synaesthesia have not yet been investigated. Here, we present the SynGenes cohort, the largest genotyped collection of unrelated people with grapheme–colour synaesthesia ( n = 723). Synaesthesia has been associated with a range of other neuropsychological traits, including enhanced memory and mental imagery, as well as greater sensory sensitivity. Motivated by the prior literature on putative trait overlaps, we investigated polygenic scores derived from published genome-wide scans of schizophrenia and autism spectrum disorder (ASD), comparing our SynGenes cohort to 2181 non-synaesthetic controls. We found a very slight association between schizophrenia polygenic scores and synaesthesia (Nagelkerke's R 2 = 0.0047, empirical p = 0.0027) and no significant association for scores related to ASD (Nagelkerke's R 2 = 0.00092, empirical p = 0.54) or body mass index ( R 2 = 0.00058, empirical p = 0.60), included as a negative control. As sample sizes for studying common genomic variation continue to increase, genetic investigations of the kind reported here may yield novel insights into the shared biology between synaesthesia and other traits, to complement findings from neuropsychology and brain imaging. This article is part of a discussion meeting issue ‘Bridging senses: novel insights from synaesthesia'.

These European Guidelines for Workplace Drug Testing in Urine have been prepared and updated by the European Workplace Drug Testing Society (EWDTS). The first version of these urine guidelines was published in 2002. Since then, the guidelines have been followed by many laboratories in different European countries and their role has been essential particularly in countries lacking legislation for workplace drug testing. In 2014, the EWDTS started a guidelines updating project and published a new version of the urine guidelines in 2015. Here we represent this updated version of the urine guidelines. The European Guidelines are designed to establish best practice procedures whilst allowing individual countries to operate within the requirements of national customs and legislation. The EWDTS recommends that all European laboratories that undertake legally defensible workplace drug testing should use these guidelines as a template for accreditation. Copyright © 2017 John Wiley & Sons, Ltd.

International audience; The role of Hartree-Fock exchange in describing the structural changes occurring upon reduction of bipyridine-based ligands and their complexes is investigated within the framework of density functional theory calculations. A set of 4 free ligands in their neutral and radical anionic forms, and 2 of their zinc complexes in their dicationic and monocationic radical forms, is used to compare a large panel of pure, conventional, and long-range corrected hybrid DFT functionals; coupled cluster single and double calculations are used alongside experimental results as benchmarks. Particular attention has been devoted to the magnitude of the change, upon reduction, of the D-parameter, which measures the difference between the Cpy-Cpy and the C-N bond lengths in bipyridine ligand and is known to experimentally correlate with the charge of the ligands. Our results indicate that the structural changes significantly depend on the amount of exact exchange included in the functional. A progressive evolution is observed for the free ligands, whereas two distinct sets of results are obtained for the complexes. Functionals with a small degree of HF exchange, e.g., B3LYP, do not adequately describe geometric changes for the considered species and, quite surprisingly, the same holds for the CC2 method. The best agreement to experimental and CCSD values is obtained with functionals that include a significant but not excessive part of exact exchange, e.g., CAM-B3LYP, M06-2X, and wB97X-D. The calculated localisation of the added electron after reduction, which depends on the self-interaction error, is used to rationalize these outcomes. Static correlation is also shown to play a role in the accurate description of electronic structure.

Synaesthesia is a neurodevelopmental trait that causes unusual sensory experiences (e.g., perceiving colours when reading letters and numbers). Our paper represents the first evidence that synaesthesia can impact negatively on children's well-being, and that there are likely to be important mental health co-morbidities for children with synaesthesia. We recruited 76 synaesthetes aged 6-10 years who had one of two types of synaesthesia (grapheme-colour synaesthesia and sequence-personality synaesthesia), and compared them to almost one thousand matched non-synaesthete controls. We tested children's wellbeing with two different measures, and found a significant relationship between synaesthesia and affect (i.e., mood), and also between synaesthesia and anxiety. Children with synaesthesia showed evidence suggesting significantly higher rates of Anxiety Disorder, and also displayed a type of mood-moderation in demonstrating fewer extremes of emotion (i.e., significantly fewer negative feelings such as fear, but also significantly fewer positive feelings such as joy). We discuss our results with reference to the emotional moderation of alexithymia (the inability to recognize or describe one's own emotions), and to a set of known links between alexithymia, anxiety, autism and synaesthesia.

Detecting the taste components within a flavoured substance relies on exposing chemoreceptors within the mouth to the chemical components of ingested food. In our paper, we show that the evaluation of taste components can also be influenced by the tactile quality of the food. We first discuss how multisensory factors might influence taste, flavour and smell for both typical and atypical (synaesthetic) populations and we then present two empirical studies showing tactile-taste interactions in the general population. We asked a group of non-synaesthetic adults to evaluate the taste components of flavoured food substances, whilst we presented simultaneous cross-sensory visuo-tactile cues within the eating environment. Specifically, we presented foodstuffs between subjects that were otherwise identical but had a rough versus smooth surface, or were served on a rough versus smooth serving-plate. We found no effect of the serving-plate, but we found the rough/smoothness of the foodstuff itself significantly influenced perception: food was rated as significantly more sour if it had a rough (versus smooth) surface. In modifying taste perception via ostensibly unrelated dimensions, we demonstrate that the detection of tastes within flavours may be influenced by higher level cross-sensory cues. Finally, we suggest that the direction of our cross-sensory associations may speak to the types of hedonic mapping found both in normal multisensory integration, and in the unusual condition of synaesthesia. © 2015.

Synaesthesia is a neurological phenomenon affecting perception, where triggering stimuli (e.g. letters and numbers) elicit unusual secondary sensory experiences (e.g. colours). Family-based studies point to a role for genetic factors in the development of this trait. However, the contributions of common genomic variation to synaesthesia have not yet been investigated. Here, we present the SynGenes cohort, the largest genotyped collection of unrelated people with grapheme–colour synaesthesia (n = 723). Synaesthesia has been associated with a range of other neuropsychological traits, including enhanced memory and mental imagery, as well as greater sensory sensitivity. Motivated by the prior literature on putative trait overlaps, we investigated polygenic scores derived from published genome-wide scans of schizophrenia and autism spectrum disorder (ASD), comparing our SynGenes cohort to 2181 non-synaesthetic controls. We found a very slight association between schizophrenia polygenic scores and synaesthesia (Nagelkerke's R(2) = 0.0047, empirical p = 0.0027) and no significant association for scores related to ASD (Nagelkerke's R(2) = 0.00092, empirical p = 0.54) or body mass index (R(2) = 0.00058, empirical p = 0.60), included as a negative control. As sample sizes for studying common genomic variation continue to increase, genetic investigations of the kind reported here may yield novel insights into the shared biology between synaesthesia and other traits, to complement findings from neuropsychology and brain imaging. This article is part of a discussion meeting issue ‘Bridging senses: novel insights from synaesthesia'.

These guidelines for Legally Defensible Workplace Drug Testing have been prepared and updated by the European Workplace Drug Testing Society (EWDTS). The European Guidelines are designed to establish best practice procedures whilst allowing individual countries to operate within the requirements of national customs and legislation. The EWDTS recommends that all European laboratories that undertake legally defensible workplace drug testing should use these guidelines as a template for accreditation. These guidelines are relevant to laboratory-based testing only. These guidelines follow current best practices and are constantly under review.

As part of a study to obtain well-defined tris(hydroxymethyl)phosphine (THP)-inspired ligands, a new nonsymmetrical diphosphine featuring two hydroxymethyl functional groups on one phosphine termin...

International audience; This work aims to improve the computation of infrared spectra of gas-phase cations using DFT methods. Experimental IRMPD spectra for ten Zn and Ru organometallic complexes have been used to provide reference data for 64 vibrational modes in the 900-2000 cm-1 range. The accuracy of the IR vibrational frequencies predicted for these bands has been assessed over five DFT functionals and three basis sets. The functionals include the popular B3LYP and M06-2X hydrids and the range-separated hybrids (RSH) CAM-B3LYP, LC-BLYP and B97X-D. B3LYP gives the best mean absolute error (MAE) and root-mean-square error (RMSE) values of 7.1 and 9.6 cm-1 , whilst the best RSH functional, B97X-D, gives 12.8 and 16.6 cm-1 respectively. Using linear correlations instead of scaling factors improves the prediction accuracy significantly for all functionals. Experimental and computed spectra for a single complex can show significant differences even when the molecular structure is calculated correctly, and a means of defining confidence limits for any given computed structure is also provided.

A chiral racemic tris(phosphaferrocene) complex showing two bridging keto functionalities has been prepared diastereoselectively through the elaboration of a single 2,5-diester-substituted phosphaferrocene. The reaction profile involves the intervention of a single trinuclear complex, which contains two phosphametallocene units and an η1-coordinated phospholyl ligand 9, whose organisation determines the stereochemistry of the final product. This complex evolves smoothly to give a chiral triphosphametallocene (±)-(R*,R*)-[2,5-(2′-CO2Me-3′,4′-Me2PC4-FeCp*)-(η5-Me2PC4)FeCp*] 10.

International audience

These European Guidelines for Workplace Drug Testing in Urine have been prepared and updated by the European Workplace Drug Testing Society (EWDTS). The first version of these urine guidelines was published in 2002. Since then, the guidelines have been followed by many laboratories in different European countries and their role has been essential particularly in countries lacking legislation for workplace drug testing. In 2014, the EWDTS started a guidelines updating project and published a new version of the urine guidelines in 2015. Here we represent this updated version of the urine guidelines. The European Guidelines are designed to establish best practice procedures whilst allowing individual countries to operate within the requirements of national customs and legislation. The EWDTS recommends that all European laboratories that undertake legally defensible workplace drug testing should use these guidelines as a template for accreditation. Copyright © 2017 John WileySons, Ltd.

We developed the Sussex Cognitive Styles Questionnaire (SCSQ) to investigate visual and verbal processing preferences and incorporate global/local processing orientations and systemising into a single, comprehensive measure. In Study 1 (N = 1542), factor analysis revealed six reliable subscales to the final 60 item questionnaire: Imagery Ability (relating to the use of visual mental imagery in everyday life); Technical/Spatial (relating to spatial mental imagery, and numerical and technical cognition); Language & Word Forms; Need for Organisation; Global Bias; and Systemising Tendency. Thus, we replicate previous findings that visual and verbal styles are separable, and that types of imagery can be subdivided. We extend previous research by showing that spatial imagery clusters with other abstract cognitive skills, and demonstrate that global/local bias can be separated from systemising. Study 2 validated the Technical/Spatial and Language & Word Forms factors by showing that they affect performance on memory tasks. In Study 3, we validated Imagery Ability, Technical/Spatial, Language & Word Forms, Global Bias, and Systemising Tendency by issuing the SCSQ to a sample of synaesthetes (N = 121) who report atypical cognitive profiles on these subscales. Thus, the SCSQ consolidates research from traditionally disparate areas of cognitive science into a comprehensive cognitive style measure, which can be used in the general population, and special populations.”

Syntheses permitting the introduction of one or two methyl substituents at the sp3-hybridized carbon atom in the backbone of enantiopure 2-phospharuthenocenemethyl phosphines are presented. Preliminary Rh-catalyzed hydrogenations of enamides suggest that the interaction of the Cp* group with the side-arm methyl group lying endo to the phosphametallocene modifies enantioselectivity significantly with respect to the side-arm- unsubstituted analogue.

Using a one-pot four-step reaction a readily available phospholide was converted efficiently to a 2-carboxyphosphole. This compound can be used as a building block for the synthesis of phosphole-containing peptides, where the phosphole can serve as a coordination site for late transition metals and may affect the secondary structure of the peptide.

People with sequence-space synaesthesia perceive sequences (e.g. numbers, months, letters) as spatially extended forms. Here, we ask whether sequence-space synaesthetes have advantages in visuo-spatial skills such as mental rotation. Previous studies addressing this question have produced mixed results with some showing mental rotation advantages (Simner et al. in Cortex 45:1246-1260, 2009; Brang et al. in Cogn Process, 2013), but one that did not (Rizza and Price in Cogn Process 13:299-303, 2012). We tested this hypothesis again with a new group of sequence-space synaesthetes, and we also tested a range of individual differences that might have caused this conflict across previous studies. Specifically, we tested: years of education, visual imagery ability, nature of forms (2D or 3D representation of sequences), number of forms (e.g. for months, days, numbers), and tendency to project sequences into external space versus the mind's eye. We found yet again that synaesthetes had enhanced abilities in mental rotation compared to controls, but that one individual difference in synaesthetes (the ability to project forms into space) was especially linked to performance. We also found that synaesthetes self-reported higher visual imagery than controls (Price in Cortex 45:1229-1245, 2009; Mann et al. in Conscious Cognit 18:619-627, 2009; Rizza and Price 2012). Overall, our data support previous studies showing superior imagery reports (Price 2009) and mental rotation (Simner et al. 2009; Brang et al. 2013) in sequence-space synaesthetes, and we suggest that one previous failure to replicate (Rizza and Price 2012) might be explained by individual differences among synaesthetes recruited for testing.

We demonstrate that the synthesis of new N-functionalized phosphinecarboxamides is possible by reaction of primary and secondary amines with PCO(-) in the presence of a proton source. These reactions proceed with varying degrees of success, and although primary amines generally afford the corresponding phosphinecarboxamides in good yields, secondary amines react more sluggishly and often give rise to significant decomposition of the 2-phosphaethynolate precursor. Of the new N-derivatized phosphinecarboxamides available, PH2C(O)NHCy (Cy = cyclohexyl) can be obtained in sufficiently high yields to allow for the exploration of its Brønsted acidity. Thus, deprotonating PH2C(O)NHCy with one equivalent of potassium bis(trimethylsilyl)amide (KHMDS) gave the new phosphide [PHC(O)NHCy](-). In contrast, deprotonation with half of an equivalent gives rise to [P{C(O)NHCy}2](-) and PH3. These phosphides can be employed to give new phosphines by reactions with electrophiles, thus demonstrating their enormous potential as chemical building blocks.

Synaesthesia is a familial condition that gives rise to unusual secondary percepts. We present a large-scale prevalence study which informs our ideas on whether the condition is more prevalent in men or women. A number of studies over the last 20 years have suggested the condition is found more commonly in women, with up to six times more female synaesthetes than male. Other studies attributed this female bias to merely a recruitment confound: women synaesthetes may be more likely to self-refer for study. We offer two pieces of evidence that there is no extreme female bias in synaesthesia: first we re-analyse previous reports of very large female biases to show again that they likely arose from self-referral or other methodological issues. Second, we present the largest published prevalence study to date on grapheme→colour synaesthesia in which our prevalence (1.39% of the population) replicates our earlier estimates (and in which we demonstrate no strong female bias even with sufficient power to detect such a difference.

International audience; Combining electron capture dissociation mass spectrometry and infrared multiple photon dissociation action spectroscopy allows the formation, selection and characterisation of reduced metal complexes containing non-innocent ligands. Zinc complexes containing diazafluorenone ligands have been studied and the localisation of the single electron on the metal atom in the mono-ligated complex has been demonstrated.

The properties of 13 monodentate P-donor ligands not previously characterised in the Ligand Knowledge Base (LKB) approach have been determined computationally, allowing their addition to the LKB-P map of ligand space.1 Consideration of ligand positions and close neighbours in ligand space can help to establish a chemical context and hence guide their application to organometallic catalysis. Here we demonstrate this potential application of the LKB-P map and discuss known and likely applications of these ligands.

International audience; A series of paramagnetic di(aryl)alkynylphosphine oxides [PF6] featuring an open-shell [Fe(κ(2)-dppe)(η(5)-C5Me5)](+) endgroup were obtained by oxidation of their neutral Fe(II) parents 3a-c, themselves obtained in a simple and nearly quantitative fashion from the corresponding Fe(II) metallophosphines 1a-c. The new organometallic radicals were characterised by NMR and ESR and were shown to be perfectly stable in solution, in contrast to species such as 1a-b[PF6] which readily dimerise.

This work expands on the recent synthesis and reactivity of the two-coordinate P(III)-containing dication [((Ph3P)2C)P(NiPr2)]2+ (3a2+). Two additional dications of general formula [((RPh2P)2C)P(NR′2)]2+ (3b2+, R = 1/2 (CH2)3, R′ = iPr; 3c2+, R = Ph, R′ = Cy) have been prepared. Solution and solid-state 31P NMR isotropic shifts for this dication class were observed around 360 ppm. Except for [3a][SbF6]2, the 31P CP/MAS NMR spectra reveal a high degree of structural disorder around the dicationic site in the solid state. Surprisingly, the synthesis of dication 3a2+ was only possible in the presence of AlCl4–, SbF6–, and substituted tetraarylborates, while the use of ClO4–, OTf–, BF4–, PF6–, and BPh4– resulted in complex product mixtures. Single-crystal X-ray analysis of dications 3a2+ and 3c2+ suggested a 4π allyl-like structure for the central CPN fragment, and this has been supported through detailed theoretical investigations. Initial reactivity studies between dications 3a2+/3c2+ and PMe3 show an equilibrium between the free dication and the target adduct. Furthermore, 3a2+ has been shown to be capable of O–H bond activation using water and methanol and polymerizes THF when it is dissolved in this solvent ASTAR (Agency for Sci., Tech. and Research, S’pore) Accepted version

7 pages Full paper; In order to try to stabilise the Tm-II ion with phospholyl ligands lacking methyl groups at the 3 and 4 positions, the following ligand precursors were prepared: sodium 2,5-di-tert-butylphospholyl [Na(Htp)] (3) and sodium 2,5-bis(trimethylsilyl)phospholyl [Na(Hsp)] (8). Because of its similar steric bulk, we also decided to use sodium di-tert-butylcyclopentadienyl jNaCp(tt) (9) as a ligand precursor. Compound 3 was obtained by sodium cleavage of the P-P bond of 2,5,2',5'-tetra- tert-butyl-1,1'-diphosphole (2). Halogen-lithium exchange in 1,4-diiodo-1,4-bis(trimethylsilyl)buta-1,3-diene (4) followed by reaction with PhPCl2 afforded 1-phenyl-2,5-bis(trimethylsilyl)phosphole (5). Treatment of 5 with lithium metal followed by oxidative treatment with iodine gave 2,5,2',5'-tetrakis(trimethylsilyl)-1,1'-diphosphole (7) which could be transformed into 8 by treatment with sodium. Treatment of 3, 8 and 9 with [TmI2(THF)(3)] in diethylether yielded three new organothulium(II) complexes [Tm(Htp)(2)(THF)] (10), [Trn(Hsp)(2)(THF)] (11) and [Tm(Cp-tt)(2)(THF)] (12), respectively, which could be isolated pure as crystalline solids in low to moderate yields. Complexes 10, 11 and 12 were studied by X-ray crystallography and their structures compared with those of two previously described complexes, [Tm(Cp")(2)(THF)] 1 [Cp" = 1,3-bis(trimethylsilyl)cyclopentadienyl] and [Tm(Dtp)(2)(THF)] (13) (Dtp = 3,4-dimethyl-2,5di-tert-butylphospholyl). Although the phospholyl ligands may be slightly more bulky than their cyclopentadienyl counterparts, the structures of 1, 10, 11 and 12 are remarkably similar and are substantially different from that of the more bulky 13. (C) Wiley-VCH Verlag GmbH and Co. KGaA, 69451 Weinheirn, Germany, 2005.

Synaesthesia is a condition that gives rise to unusual secondary sensations (e.g., colours are perceived when listening to music). These unusual sensations tend to be reported as being stable throughout adulthood (e.g., Simner & Logie, 2007, Neurocase, 13, 358) and the consistency of these experiences over time is taken as the behavioural hallmark of genuineness. Our study looked at the influence of mood states on synaesthetic colours. In Experiment 1, we recruited grapheme-colour synaesthetes (who experience colours from letters/digits) and elicited their synaesthetic colours, as well as their mood and depression states, in two different testing sessions. In each session, participants completed the PANAS-X (Watson & Clark, 1999) and the BDI-II (Beck, Steer, & Brown, 1996, Manual for Beck Depression Inventory-II), and chose their synaesthetic colours for letters A-Z from an interactive colour palette. We found that negative mood significantly decreased the luminance of synaesthetic colours. In Experiment 2, we showed that synaesthetic colours were also less luminant for synaesthetes with anxiety disorder, versus those without. Additional evidence suggests that colour saturation, too, may inversely correlate with depressive symptoms. These results show that fluctuations in mood within both a normal and clinical range influence synaesthetic colours over time. This has implications for our understanding about the longitudinal stability of synaesthetic experiences, and of how mood may interact with the visual (imagery) systems. © 2014 The British Psychological Society.

International audience; The redox-active metallaphosphine [Fe(dppe)(η(5)-C5Me5)(C≡C-PPh2)] reacts with [Pd(1,5-cod)Cl2] to give mono- and bis-phosphine coordinated palladium centres as a function of stoichiometry, and these complexes provide a stable redox-active platform which allows reversible one-electron {Fe(II)→Fe(III)(+)} oxidations within the palladium coordination sphere.

Using a combination of electrochemical and NMR techniques, the oxidative addition of PhX to three closely related bis-diphosphine P2Pd(0) complexes, where the steric bulk of just one substituent was varied, has been analysed quantitatively. For the complex derived from MetBu2P, a rapid reaction ensued with PhI following an associative mechanism, and data was also obtained by cyclic voltammetry for PhOTs, PhBr and PhCl, revealing distinct relative reactivities from the related (PCx3)2Pd complex (Cx = cyclohexyl) previously studied. The corresponding EttBu2P complex reacted more slowly with PhI and was studied by NMR spectroscopy. The reaction course indicated a mixture of pathways, with contribution from a component that was [PhI] independent. For the CxtBu2P complex, reaction was again monitored by NMR spectroscopy, and was even slower. At high PhI concentrations reaction was predominantly linear in [PhI], but at lower concentrations the [PhI] independent pathway was again observed, and an accelerating influence of the reaction product was observed over the concentration range. The NMR spectra of the EttBu2P and CxtBu2P complexes conducted in C6D6 shows some line broadening that was augmented on addition of PhI. NMR experiments carried out in parallel show that there is rapid ligand exchange between free phosphine and the Pd2Pd complex and also a slow ligand crossover between different P2Pd complexes. DFT calculations were carried out to further test the feasibility of C6D6 involvement in the oxidative addition process, and located Van der Waals complexes for association of the P2Pd(0) complexes with either PhI or benzene. PhI or solvent-assisted pathways for ligand loss are both lower in energy than direct ligand dissociation. Taken all together, these results provide a consistent explanation for the surprising complexity of an apparently simple reaction step. The clear dividing line between reactions that give a di- or monophosphine palladium complex after oxidative addition clarifies the participation of the ligand in coupling catalysis.

Synesthesia is an inherited condition causing unusual secondary sensations (e.g, sounds might be experienced as both auditory and visual percepts). The condition has been linked with cognitive and perceptual benefits and is considered a benign alternative form of perception. Here, we investigate self-referred synesthete populations and their rates of radiologically determined white matter hyperintensities (WMH) of a type compatible with the McDonald imaging criteria for the diagnosis of multiple sclerosis (MS). MS is a chronic condition resulting in damage to myelination surrounding nerve fibers of the central nervous system (CNS). Magnetic resonance imaging (MRI) features highly suggestive of MS without overt clinical symptoms are termed radiologically isolated syndrome (RIS). We present data showing that the shared MRI profile of MS and RIS has been significantly overrepresented in synesthetes who have participated in neuroimaging research. We present validation of the clinical and MRI status of these synesthetes and an analysis showing the significant probability their unusual numbers may not have arisen by chance. We discuss how to interpret significant data based on small case numbers and consider the implications of our findings for synesthesia’s clinical status.

International audience; Using the σ- and п-donating properties of carbodiphosphorane ligands, we recently synthesized a phosphorus (III)-containing dication. It is observed to undergo interesting reactivity with PMe3, H2O and MeOH.

The solid state structure of h5-2,5-di-(t-butyl)phospholylgallium(I) 1 was detd. by x-ray diffraction at 190 K. The mols. of 1 are partly organized in a new type of structure: a Ga zigzag chain in which the arom. phospholyl rings alternate on both sides of the chain. [on SciFinder (R)]

International audience; The present review covers the preparations of 1-alkynylphosphonates by Michaelis-Arbuzov and Michaelis-Becker reactions, nucleophilic substitutions at phosphorus (SNP(V)) and elimination from 1-alkenylphosphonates. Their reactivity and versatility have made them valuable precursors for other phosphonates and particularly for the synthesis of heterocycles by [2+2], [3+2] and [4+2] cycloaddition reactions.

Monomeric polyhapto-bound phospholyl compounds were hitherto unknown for the main group elements. Use of a solution of metastable GaBr has allowed the synthesis of monomeric η5 -phospholylgallium, which has been characterized by X-ray structure analysis as the Cr(CO)5 complex 1.

Thermolysis of 2,2‘,5,5‘-tetra-tert-butyl-1,1‘-biphosphole with Co2(CO)8 gives good yields of (2,5-di-tert-butylphospholyl)dicarbonylcobalt (1), a compound which provided access to a range of cobalt phospholyl complexes. Thermolysis with trimethyl phosphite produced C12H20PCo(CO)P(OMe)3 (2), while photolysis with 1,3-cyclohexadiene and 1,5-cyclooctadiene gave the corresponding complexes C12H20PCo(diene) (3, 4). In the absence of a donor ligand, a metal−metal doubly bridged dimer 6 was obtained; this reacted classically with ethyl diazoacetate to give the bridging complex {C12H20PCo(CO)}2(μ-CHCO2Et) (7). Prolonged heating of 1 with 3-hexyne in xylene gave the cyclotrimerization product C6Et6; an initial attempt to prepare pyridines by cocyclization of PrCN with PhC⋮CΗ gave the cyclobutadiene complex C12H20PCo(1,2-C4H2Ph2) (5).

Synesthesia is a hereditary, neurological condition in which a wide range of common stimuli (e.g., letters, sounds, flavors) trigger unexpected secondary sensations, for example, synesthetes listening to music might see colors in addition to hearing sounds (Ward et al., 2006; see Simner and Hubbard, 2013, for review). Current explanations of synesthesia posit structural and/or functional differences in the synesthete brains, and frame their models in terms of excess cortical connectivity or altered cortical feedback. Here, we propose an immune hypothesis of synesthesia, which supplements existing models by suggesting how such altered connectivity may arise and how associations between synesthesia and other conditions might be explained. Two categories of model seek to explain the generation of synesthetic experiences, and more recent models are a hybrid of both (Brang et al., 2010). The cross-activation model (Ramachandran and Hubbard, 2001) suggests that excess connectivity between functional areas of the cortex allows activation in one cortical area (e.g., auditory cortex) to directly trigger activation in another (e.g., visual cortex). Evidence in support of this model comes for example from diffusion tensor imaging (DTI) and shows that excessive connectivity is indeed a feature of the synesthetic brain (Rouw and Scholte, 2007). Re-entrant and disinhibited feedback models propose that synesthetic sensations are caused by disinhibited feedback from higher cortical areas (e.g., in parietal lobe) failing to suppress non-relevant activation from lower cortical areas (Grossenbacher and Lovelace, 2001). This type of disinhibited feedback may result from excessive activity of excitatory neurons within the delicate balance between both excitatory and inhibitory neurons in the brain (Hubbard et al., 2011). Despite appearing superficially different, connectivity and feedback models need not be mutually exclusive. It is unlikely that altered feedback happens entirely in the absence of changes in cortical connectivity, given the Hebbian principle that simultaneous activity strengthens interconnectivity between neurons. Therefore, these two approaches might be considered somewhat unified in that connectivity models propose aberrant connectivity as the primary causal mechanism underlying synesthesia whereas feedback models might allow altered connectivity as an indirect consequence of disinhibited feedback. While these models are now more than a decade old, explanations of how these cortical characteristics might arise have proven elusive thus far (but see Brang and Ramachandran, 2008; Mitchell, 2013) and we explore this here. Synesthesia is thought to be primarily neurodevelopmental in nature (Spector and Maurer, 2009). Consequentially, known processes of brain development are likely to be implicated in its emergence. We propose that insight might be gained from examining the functionality of genes that regulate the types of altered synesthetic cortical connectivity assumed in these models above (i.e., genes for axon guidance, synapse density). This is the approach we follow here.

International audience; A double ring-expansion methodology allows the stepwise synthesis of tri- and tetra-phosphaporhyrinogens. Structural and calculational methods reveal extended delocalisation about their phospholide centres.

An electrochemically switched face inversion process for η(5)-coordinated ligands in late transition metal sandwich complexes is demonstrated.

[PdL 2 ] -catalyzed (L=triphenyl- or trifurylphosphine) cross-coupling of 2,4,6-tribromo- or 2,6-dibromophosphinines with R-SnMe 3 derivatives yields the corresponding 2,6-di-R-phosphinines, where R=2-furyl, 2-thienyl, 2-N-methylpyrrolyl, or C≡C-Ph. When R is 2-pyridyl, only the monosubstituted phosphinine is obtained. A similar cross-coupling reaction between 2,4,6-tribromo- or 2-bromophosphinines and (trimethylsilyl)diphenylphosphine gives either 2,6-bis(diphenylphosphino)- or 2-(diphenylphosphino)phosphinines according to the starting materials. In the case of 2,4,6-tribromophosphinines, the ortho selectivity of the functionalizations probably reflects an initial coordination of [PdL 2 ] to the phosphinine phosphorus

Some recent developments in the chemistry of phosphinines are discussed. They include a one pot synthesis of C- polybrominated phosphinines through direct bromination of the phosphinine ring and a preliminary investigation of the reactivity of these species.

The reaction of (E)- and (Z)-[W(CO)5( [graphic omitted]HPh)] complexes with [M(PR3)2(C2H4)][M = Pd, (PR3)2= dppe (Ph2PCH2CH2PPh2); M = Pt, PR3= PPh3] has been studied and the following products [which result from insertion of the M(PR3)2 frogment into the phosphirane ring] have been fully characterised by NMR spectroscopy: (2R*,3S*,4S*)-(±)-, (2R*,3S*,4R*)-(±)- and (2R*,3S*,4R*)-(±)-[(dppe) Pd(CHPhCHPhPPh)W(CO)5]; (2S*,3S*,4S*)-(±)-, (2S*3R*4R*)-(±)- and (2S*,3S*,4R*)-(±)-[(Ph3P)2Pt(CHPhCHPhPPh)W(CO)5]; and trans-(2S*,3S*,4R*)-(±)-[(Ph3P)(OC)Pt-(CHPhCHPhPPh)W(CO)5]. The crystal and molecular structures of (Z)-[W(CO)5([graphic omitted]HPh)], (2R*,3S*,4R*)-(±)- and (R*,3S*,4S*)-(±)-[(dppe)Pd(CHPhCHPhPPh)W(CO)5] have been determined. The configurations of the products are interpreted in terms of a transition state in which a P–C bond is η2-co-ordinated to M(PR3)2 fragment.