Radical C?H Arylation of the BODIPY Core with Aryldiazonium Salts: Synthesis of Highly Fluorescent Red‐Shifted Dyes

We describe herein the first radical C H arylation of BODIPY dyes. This novel, general, one‐step synthetic procedure uses ferrocene to generate aryl radical species from aryldiazonium salts and allows the straightforward synthesis of brightly fluorescent (Φ>0.85) 3,5‐diarylated and 3‐monoarylated boron dipyrrins in up to 86 % yield for a broad range of aryl substituents. In this way, new and complex dyes with red‐shifted spectra can be easily prepared.     

Computationally efficient evaluation of appointment schedules in health care

We consider the problem of evaluating and constructing appointment schedules for patients in a health care facility where a single physician treats patients in a consecutive manner, as is common for general practitioners, clinics and for outpatients in hospitals. Specifically, given a fixed-length session during which a physician sees K patients, each patient has to be given an appointment time during this session in advance. Optimising a schedule with respect to patient waiting times, physician idle times, session overtime, etc. usually requires a heuristic search method involving a huge number of repeated schedule evaluations. Hence, our aim is to obtain accurate predictions at very low computational cost. This is achieved by (1) using Lindley’s recursion to allow for explicit expressions and (2) choosing a discrete-time (slotted) setting to make those expressions easy to compute. We assume general, possibly distinct, distributions for the patients’ consultation times, which allows to account for multiple treatment types, emergencies and patient no-shows. The moments of waiting and idle times are obtained and the computational complexity of the algorithm is discussed. Additionally, we calculate the schedule’s performance in between appointments in order to assist a sequential scheduling strategy.     

Conservative independence-based causal structure learning in absence of adjacency faithfulness

This paper presents an extension to the Conservative PC algorithm which is able to detect violations of adjacency faithfulness under causal sufficiency and triangle faithfulness. Violations can be characterized by pseudo-independent relations and equivalent edges, both generating a pattern of conditional independencies that cannot be modeled faithfully. Both cases lead to uncertainty about specific parts of the skeleton of the causal graph. These ambiguities are modeled by an f-pattern. We prove that our Adjacency Conservative PC algorithm is able to correctly learn the f-pattern. We argue that the solution also applies for the finite sample case if we accept that only strong edges can be identified. Experiments based on simulations and the ALARM benchmark model show that the rate of false edge removals is significantly reduced, at the expense of uncertainty on the skeleton and a higher sensitivity for accidental correlations.     

Direct electroplating of copper on tantalum from ionic liquids in high vacuum: origin of the tantalum oxide layer

In this paper, it is shown that high vacuum conditions are not sufficient to completely remove water and oxygen from the ionic liquid 1-ethyl-3-methylimidazolium chloride. Complete removal of water demands heating above 150 °C under reduced pressure, as proven by Nuclear Reaction Analysis (NRA). Dissolved oxygen gas can only be removed by the use of an oxygen scavenger such as hydroquinone, despite the fact that calculations show that oxygen should be removed completely by the applied vacuum conditions. After applying a strict drying procedure and scavenging of molecular oxygen, it was possible to deposit copper directly on tantalum without the presence of an intervening oxide layer.     

Oscillating electrochemical reaction in copper-containing imidazolium ionic liquids

An example of an electrochemical oscillator in ionic liquids is presented. Solutions of the ionic liquid 1-ethyl-3-methylimidazolium chloride, [C(2)mim]Cl, which contain both Cu(+) and Cu(2+) ions, show current oscillations during potentiostatic polarization. The oscillations were analyzed by the Quartz Crystal Microbalance (QCM) technique and by Electrochemical Impedance Spectroscopy (EIS). The electrochemical oscillations are of the N-NDR-type, because the low frequency end of the impedance spectrum has negative real impedances. The oscillating current leads to an oscillating growth speed of a metallic copper layer. Besides the presence of both Cu(+) and Cu(2+), the presence of chloride is a necessary, yet not a sufficient, condition for the occurrence of current oscillations. Oscillating currents were also observed for the ionic liquids 1-butyl-3-methylimidazolium chloride and 1-butyl-2,3-dimethylimidazolium chloride, but not for tributyltetradecylphosphonium chloride and N-butylpyridinium chloride.