Photoinduced Ullmann C–N Coupling: Demonstrating the Viability of a Radical Pathway

Carbon–nitrogen (C–N) bond-forming reactions of amines with aryl halides to generate arylamines (anilines), mediated by a stoichiometric copper reagent at elevated temperature (>180°C), were first described by Ullmann in 1903. In the intervening century, this and related C–N bond-forming processes have emerged as powerful tools for organic synthesis. Here, we report that Ullmann C–N coupling can be photoinduced by using a stoichiometric or a catalytic amount of copper, which enables the reaction to proceed under unusually mild conditions (room temperature or even –40°C). An array of data are consistent with a single-electron transfer mechanism, representing the most substantial experimental support to date for the viability of this pathway for Ullmann C–N couplings

Sleeping Beauty: Anesthesia May Promote Relapse in Dogs With Diffuse Large B-Cell Lymphoma in Complete Remission After Chemo-Immunotherapy

Surgery-induced stress and anesthesia-related immunosuppression are believed to play a critical role in human oncology patients. Studies have hypothesized that anesthesia influences patients' outcome, promoting tumor recurrence and metastasis. Aim of the study was to investigate whether anesthesia promoted relapse in dogs with diffuse large B-cell lymphoma (DLBCL). Medical records were searched for dogs with DLBCL, that were in complete remission (CR) after the same chemo-immunotherapy protocol. Dogs receiving anesthesia were included if the procedure was performed while in CR. Time to relapse (TTR) was obtained via Kaplan–Meier method. Association between anesthesia and relapse was assessed using a nested case-control design and estimated using conditional logistic regression. Sixty-one dogs with DLBCL were included. Overall median TTR was 329 days (95% CI, 281–377). Forty-eight (79%) dogs relapsed during the study period, while 13 (21%) were still in CR at data analysis closure. Eighteen (30%) dogs received anesthesia with opioids, propofol, and isoflurane or sevoflurane. The relative risk of lymphoma relapse for dogs undergoing anesthesia was significantly higher compared with dogs not undergoing anesthesia, with an odds ratio of 3.09 (P = 0.019) on multivariable analysis. Anesthesia may promote relapse in dogs with DLBCL treated with chemo-immunotherapy, although a role of perioperative stress cannot be ultimately excluded. Considering the high frequency of anesthetic procedures required for diagnostic and therapeutic protocols among oncology patients, it is of utmost interest to characterize the effects of single anesthetic agents on the immune system. Further prospective studies are needed to better define the impact of anesthesia on patients' outcome

Serum Oxytocin, Cortisol and Social Behavior in Calves: A Study in the Impossible Task Paradigm

In this study, we explored the correlations between circulating levels of oxytocin, cortisol, and different social behaviors toward humans in 26 Italian Red Pied calves (all females, with an average age of 174 ± 24 days) using the impossible task paradigm. This paradigm has proved fruitful in highlighting the effect of socialization on the willingness to interact with humans in several domesticated species. The test consists of the violation of an expectation (recovering food from an experimental apparatus) while a caregiver and a stranger are present. Immediately after the end of the test (less than one minute), blood was collected from the coccygeal vein. Statistics were performed by the Spearman’s rank correlation; significant differences were adjusted according to Bonferroni’s correction. Cortisol correlates positively (ρ = 0.565; p < 0.05) with the latency of behaviors directed at the caregiver, and the duration of behaviors directed at the apparatus correlates negatively with both the caregiver (ρ = −0.654; p < 0.05) and a stranger (ρ = −0.644; p < 0.05). Contrary to what is reported in the literature on cows, no correlations were found between oxytocin levels and direct behaviors toward the caregiver. This highlights a different behavioral strategy between calves and cows when placed in front of an impossible task

Fully Metal-Coated Scanning Near-Field Optical Microscopy Probes with Spiral Corrugations for Superfocusing under Arbitrarily Oriented Linearly Polarised Excitation

We study the effect of a spiral corrugation on the outer surface of a fully metal-coated scanning near-field optical microscopy (SNOM) probe using the finite element method. The introduction of a novel form of asymmetry, devoid of any preferential spatial direction and covering the whole angular range of the originally axisymmetric tip, allows attaining strong field localization for a linearly polarised mode with arbitrary orientation. Compared to previously proposed asymmetric structures which require linearly polarised excitation properly oriented with respect to the asymmetry, such a configuration enables significant simplification in mode injection. In fact, not only is the need for the delicate procedure to generate radially polarised beams overcome, but also the relative alignment between the linearly polarised beam and the tip modification is no longer critical

A quantitative description of the transition between intuitive altruism and rational deliberation in iterated Prisoner's Dilemma experiments

What is intuitive: pro-social or anti-social behaviour? To answer this fundamental question, recent studies analyse decision times in game theory experiments under the assumption that intuitive decisions are fast and that deliberation is slow. These analyses keep track of the average time taken to make decisions under different conditions. Lacking any knowledge of the underlying dynamics, such simplistic approach might however lead to erroneous interpretations. Here we model the cognitive basis of strategic cooperative decision making using the Drift Diffusion Model to discern between deliberation and intuition and describe the evolution of the decision making in iterated Prisoner's Dilemma experiments. We find that, although initially people's intuitive decision is to cooperate, rational deliberation quickly becomes dominant over an initial intuitive bias towards cooperation, which is fostered by positive interactions as much as frustrated by a negative one. However, this initial pro-social tendency is resilient, as after a pause it resets to the same initial value. These results illustrate the new insight that can be achieved thanks to a quantitative modelling of human behavior

Beliefs about others' intentions determine whether cooperation is the faster choice

Is collaboration the fast choice for humans? Past studies proposed that cooperation is a behavioural default, based on Response Times (RT) findings. Here we contend that the individual’s reckoning of the immediate social environment shapes her predisposition to cooperate and, hence, response latencies. In a social dilemma game, we manipulate the beliefs about the partner’s intentions to cooperate and show that they act as a switch that determines cooperation and defection RTs; when the partner’s intention to cooperate is perceived as high, cooperation choices are speeded up, while defection is slowed down. Importantly, this social context effect holds across varying expected payoffs, indicating that it modulates behaviour regardless of choices’ similarity in monetary terms. Moreover, this pattern is moderated by individual variability in social preferences: Among conditional cooperators, high cooperation beliefs speed up cooperation responses and slow down defection. Among free-riders, defection is always faster and more likely than cooperation, while high cooperation beliefs slow down all decisions. These results shed new light on the conflict of choices account of response latencies, as well as on the intuitive cooperation hypothesis, and can help to correctly interpret and reconcile previous, apparently contradictory results, by considering the role of context in social dilemmas

Elevated serum levels of soluble CD154 in children with juvenile idiopathic arthritis

<p>Abstract</p> <p>Objective</p> <p>Cytokines play important roles in mediating inflammation in autoimmunity. Several cytokines are elevated in serum and synovial fluid samples from children with Juvenile Idiopathic Arthritis (JIA). Soluble CD154 (sCD154) is elevated in other autoimmune disorders, but has not been characterized in JIA. Our objectives were to determine if sCD154 is elevated in JIA, and to examine correlations between sCD154 and other inflammatory cytokines.</p> <p>Methods</p> <p>Serum from 77 children with JIA and 81 pediatric controls was analyzed for interleukin (IL)1β, IL2, IL4, IL5, IL6, IL8, IL10, IL12, IL13, sCD154, interferon-γ (IFNγ), soluble IL2 receptor (sIL2R), and tumor necrosis factor-α (TNFα), using the Luminex Multi-Analyte Profiling system. Differences in levels of cytokines between cases and controls were analyzed. Logistic regression was also performed.</p> <p>Results</p> <p>sCD154 was significantly elevated in cases compared to controls (p < 0.0001). IL1β, IL5, IL6, IL8, IL13, IFNγ, sIL2R, and TNFα were also significantly elevated in JIA. Levels of sCD154 were highly correlated with IL1β, IL6, IL8, and TNFα (p < 0.0001). Logistic regression analysis suggested that IL6 (odds ratio (OR): 1.4, p < 0.0001), sCD154 (OR: 1.1, p < 0.0001), and TNFα (OR: 1.1, p < 0.005) were positively associated with JIA, while IL10 (OR: 0.5, p < 0.002) was protective. sCD154 was elevated in all JIA subtypes, with highest levels among more severe subtypes. IL1β, IL6, IL8, sIL2R and TNFα were also elevated in several JIA subtypes.</p> <p>Conclusion</p> <p>Serum levels of sCD154, IL1β, IL6, IL8, sIL2R and TNFα are elevated in most JIA subtypes, suggesting a major role for sCD154, and these cytokines and cytokine receptors in the pathogenesis of JIA.</p

Strong, bold, and kind : Self-control and cooperation in social dilemmas

Financial support from the Swedish Research Council (Vetenskapsrådet), from Formas through the program Human Cooperation to Manage Natural Resources (COMMONS), and the Ideenfonds of the University of Munich is gratefully acknowledged.We develop a model that relates self-control to cooperation patterns in social dilemmas, and we test the model in a laboratory public goods experiment. As predicted, we find a robust association between stronger self-control and higher levels of cooperation, and the association is at its strongest when the decision maker’s risk aversion is low and the cooperation levels of others high. We interpret the pattern as evidence for the notion that individuals may experience an impulse to act in self-interest—and that cooperative behavior benefits from self-control. Free-riders differ from other contributor types only in their tendency not to have identified a self-control conflict in the first place.PostprintPeer reviewe

IL-27 Regulates IL-18 Binding Protein in Skin Resident Cells

IL-18 is an important mediator involved in chronic inflammatory conditions such as cutaneous lupus erythematosus, psoriasis and chronic eczema. An imbalance between IL-18 and its endogenous antagonist IL-18 binding protein (BP) may account for increased IL-18 activity. IL-27 is a cytokine with dual function displaying pro- and anti-inflammatory properties. Here we provide evidence for a yet not described anti-inflammatory mode of action on skin resident cells. Human keratinocytes and surprisingly also fibroblasts (which do not produce any IL-18) show a robust, dose-dependent and highly inducible mRNA expression and secretion of IL-18BP upon IL-27 stimulation. Other IL-12 family members failed to induce IL-18BP. The production of IL-18BP peaked between 48–72 h after stimulation and was sustained for up to 96 h. Investigation of the signalling pathway showed that IL-27 activates STAT1 in human keratinocytes and that a proximal GAS site at the IL-18BP promoter is of importance for the functional activity of IL-27. The data are in support of a significant anti-inflammatory effect of IL-27 on skin resident cells. An important novel property of IL-27 in skin pathobiology may be to counter-regulate IL-18 activities by acting on keratinocytes and importantly also on dermal fibroblasts