A Brief Version of the Implicit Positive and Negative Affect Test (IPANAT-18).

As self-reports of affect are limited in several regards, an indirect measure of affect, the Implicit Positive and Negative Affect Test (IPANAT; Quirin, Kazén, & Kuhl, 2009) has previously been developed and adapted to more than 10 languages (Quirin et al., 2018), showing adequate reliability and validity. Based on a sample of 242 Spanish adults (111 males), we evaluate a trimmed 18 items version of the IPANAT (IPANAT-18). Item reductive procedures consisted in a random selection of the stimuli words used in the IPANAT. Psychometric properties of the IPANAT-18 were evaluated via Confirmatory Factor Analysis. In addition, correlational analyses were used to determine the relationship between the brief and the full version of the IPANAT, and with explicit measures of affect. We replicated a two-factors structure of positive affect versus negative affect and found a good fit for the IPANAT-18 model (CFI = 1; TLI = 1; RMSEA = .00; SRMR = .03). Reliability was adequate (implicit PA, α = .86; implicit NA, α = .77) and the pattern of relationships with explicit affect measures were congruent and consistent with previous findings. Differences between the mean scores of implicit affect assessed with 18 items or 36 items were statistically non-significant, and showed strong correlations (PA, r = .92, p < .01; NA, r = .88, p < .01). In sum, the IPANAT-18 showed satisfactory psychometric properties and constitutes a useful tool for economically measuring affective processes such as in experimental and economical multiple assessment (e.g., daily diary) settings.

Alterations in the fronto-limbic network and corpus callosum in borderline-personality disorder.

Neuroimaging research provides evidence of grey matter changes in the prefrontal-limbic network in borderline personality disorder (BPD), yet research scarcely examines the white matter (WM) within this circuitry. The present study aimed to explore WM in prefrontal-limbic brain networks within BPD. Quantitative diffusion tensor imaging (DTI-MRI) measures of fractional anisotropy (FA) and mean diffusion (MD) were used to analyze the neural pathways in fifteen individuals with BPD (M = 25, SD = 6.76), in comparison to thirteen healthy individuals (M = 27.92, SD = 8.41). Quantitative DTI-MRI measures of FA and MD were evaluated for the cingulum, the fornix, the corpus callosum (CC), the inferior longitudinal fasciculus (ILF), the superior longitudinal fasciculus (SLF) and the uncinate fasciculus (UF). Lower FA values for both the left and the right cingulum, the genu, body, and splenium of the CC, left ILF and right SLF were found in BPD, compared to healthy individuals. MD values were higher for the genu and splenium of the CC in BPD. The findings indicate that a large-scale emotional brain network is affected in BPD with alterations in MD and FA of WM prefrontal-limbic pathways of the heteromodal association cortex involved in emotion processing and emotion regulation.

Asymmetric copper-catalyzed C-N cross-couplings induced by visible light.

Despite a well-developed and growing body of work in copper catalysis, the potential of copper to serve as a photocatalyst remains underexplored. Here we describe a photoinduced copper-catalyzed method for coupling readily available racemic tertiary alkyl chloride electrophiles with amines to generate fully substituted stereocenters with high enantioselectivity. The reaction proceeds at -40°C under excitation by a blue light-emitting diode and benefits from the use of a single, Earth-abundant transition metal acting as both the photocatalyst and the source of asymmetric induction. An enantioconvergent mechanism transforms the racemic starting material into a single product enantiomer.

Synthesis of functionalized, dispersible carbon-coated cobalt nanoparticles for potential biomedical applications.

Ferromagnetic carbon-coated cobalt nanoparticles have been ligated by a covalent or non-covalent strategy with dendrons or polymers bearing amino-, hydroxy- or polyether-functionalities, aiming at synthesizing materials that are dispersible in aqueous solutions, being a prerequisite for applications in biomedicine. Most efficiently for this purpose proved to be a covalently anchored polyethyleneimine (PEI) with a loading of approximately 10 mmol of amino groups per gram of hybrid nanomaterial, resulting in dispersions that are stable in water for several days.

Does unconscious stress play a role in prolonged cardiovascular stress recovery?

According to recent insights, humans might not be aware of a substantial part of their cognitive stress representations while these still have prolonged physiological effects. 'Unconscious stress' can be measured by implicit affect (IA) tests. It was shown that IA predicts physiological stress responses, in fact better than explicit ('conscious') affect. It is not known yet whether IA is associated with concurrent prolonged stress responses. In two studies (n = 62 and 123), anger harassment was used to induce stress. Blood pressure (BP) and heart rate (HR) were measured continuously. During BP and HR recovery, IA was measured by an 'anger' version of the implicit association test (IAT) or the implicit positive and negative affect test (IPANAT). Blood pressure and HR increased during anger harassment and recovery afterwards. When using the IPANAT BP recovery levels were lower when positive IA was high and higher when negative IA was high, independent of explicit affect and rumination. These results were not found using the IAT. These results provide preliminary evidence that physiological stress recovery is associated with IA. This is in line with the theory that unconscious stress is responsible for a-possibly considerable-part of unhealthy prolonged stress-related physiological activity.

Polymer- and dendrimer-coated magnetic nanoparticles as versatile supports for catalysts, scavengers, and reagents.

The work-up of chemical reactions by standard techniques is often time consuming and energy demanding, especially when chemists have to guarantee low levels of metal contamination in the products. Therefore, scientists need new ideas to rapidly purify reaction mixtures that are both economically and environmentally benign. One intriguing approach is to tether functionalities that are required to perform organic reactions to magnetic nanoparticles, for example, catalysts, reagents, scavengers, or chelators. This strategy allows researchers to quickly separate active agents from reaction mixtures by exploiting the magnetic properties of the support. In this Account, we discuss the main attributes of magnetic supports and describe how we can make the different nanomagnets accessible by surface functionalization. Arguably the most prominent magnetic nanoparticles are superparamagnetic iron oxide nanoparticles (SPIONs) due to their biologically well-accepted constituents, their established size-selective synthesis methods, and their diminished agglomeration (no residual magnetic attraction in the absence of an external magnetic field). However, nanoparticles made of pure metal have a considerably higher magnetization level that is useful in applications where high loadings are needed. A few layers of carbon can efficiently shield such highly reactive metal nanoparticles and, equally important, enable facile covalent functionalization via diazonium chemistry or non-covalent functionalization through π-π interactions. We highlight carbon-coated cobalt (Co/C) and iron (Fe/C) nanoparticles in this Account and compare them to SPIONs stabilized with surfactants or silica shells. The graphene-like coating of these nanoparticles offers only low loadings with functional groups via direct surface modification, and the resulting nanomagnets are prone to agglomeration without effective steric stabilization. To overcome these restrictions and to tune the dispersibility of the magnetic supports in different solvents, we can introduce dendrimers and polymers on Co/C and Fe/C platforms by various synthetic strategies. While dendrimers have the advantage of being able to array all functional groups on the surface, polymers need fewer synthetic steps and higher molecular weight analogues are easily accessible. We present the application of these promising hybrid materials for the extraction of analytes or contaminates from complex aqueous solutions (e.g. waste water treatments or blood analytics), for metal-, organo-, and biocatalysis, and in organic synthesis. In addition, we describe advanced concepts like magnetic protecting groups, a multistep synthesis solely applying magnetic reagents and scavengers, and thermoresponsive self-separating magnetic catalysts. We also discuss the first examples of the use of magnetic scaffolds manipulated by external magnetic fields in flow reactors on the laboratory scale. These hold promise for future applications of magnetic hybrid materials in continuous flow or highly parallelized syntheses with rapid magnetic separation of the applied resins.

Synthesis of trisubstituted ureas by a multistep sequence utilizing recyclable magnetic reagents and scavengers.

Unprecedented magnetic borohydride exchange (mBER), magnetic Wang aldehyde (mWang) and magnetic amine resins were prepared from highly magnetic polymer-coated cobalt or iron nanoparticles. Microwave irradiation was used to obtain excellent degrees of functionalization (>95 %) and loadings (up to 3.0 mmol g(-1)) in short reaction times of 15 min or less. A small library of ureas and thioureas was synthesized by the exclusive application of these magnetic resins. As a first step, a reductive amination of aromatic and aliphatic aldehydes was carried out with mBER. The excess of primary amine needed to complete the reaction was subsequently scavenged selectively by mWang. Simple magnetic decantation from the resins resulted in secondary amines in good to excellent yields and purities. The used magnetic resins were efficiently regenerated and reused for the next run. In a second step, the secondary amines were converted to trisubstituted (thio)ureas in excellent yields and purities by stirring with an excess of iso(thio)cyanate, which was scavenged by addition of the magnetic amine resin after completion of the reaction. The whole reaction sequence is carried out without any purification apart from magnetic decantation; moreover, conventional magnetic stirring can be used as opposed to the vortexing required for polystyrene resins.

Ring-opening metathesis polymerization-based recyclable magnetic acylation reagents.

An operationally simple method for the acylation of amines utilizing carbon-coated metal nanoparticles as recyclable supports is reported. Highly magnetic carbon-coated cobalt (Co/C) and iron (Fe/C) nanobeads were functionalized with a norbornene tag (Nb-tag) through a "click" reaction followed by surface activation employing Grubbs-II catalyst and subsequent grafting of acylated N-hydroxysuccinimide ROMPgels (ROMP=ring-opening metathesis polymerization). The high loading (up to 2.6 mmolg(-1) ) hybrid material was applied in the acylation of various primary and secondary amines. The products were isolated in high yields (86-99%) and excellent purities (all >95 % by NMR spectroscopy) after rapid magnetic decantation and simple evaporation of the solvents. The spent resins were successfully re-acylated by acid chlorides, anhydrides, and carboxylic acids and reused for up to five consecutive cycles without considerable loss of activity.

Intramolecular monomer-on-monomer (MoM) Mitsunobu cyclization for the synthesis of benzofused thiadiazepine-dioxides.

The utilization of a monomer-on-monomer (MoM) intramolecular Mitsunobu cyclization reaction employing norbornenyl-tagged (Nb-tagged) reagents is reported for the synthesis of benzofused thiadiazepine-dioxides. Facile purification was achieved via ring-opening metathesis (ROM) polymerization initiated by one of three metathesis catalyst methods: (i) free metathesis catalyst, (ii) surface-initiated catalyst-armed silica, or (iii) surface-initiated catalyst-armed Co/C magnetic nanoparticles.