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Creators/Authors contains: "Wolf, Christian"

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  1. The reaction between a chiral carboxylic acid molecule and 1,1′-bis(diphenylphosphino)ferrocenepalladium dichloride in the presence of a mild base generates a chiroptically active metal complex displaying strong CD signals in the visible light region, a highly sought-after goal in the optical sensing realm. The molecular recognition process is complete within a few minutes and can be used for fast chiroptical determination of the enantiomeric composition and concentration of carboxylic acid samples. This method is operationally simple and broadly applicable to a large variety of structures including important drugs, natural products, amino acids and hydroxy acids. All components needed are commercially available and this optical sensing assay can be readily adapted by any laboratory interested in chirality analysis and high-throughput experimentation. 
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  2. Chiroptical sensing of nitriles is achieved with excellent functional group tolerance by hydrozirconation and subsequent transmetalation of the corresponding iminate to a chromophoric palladium complex. A one-pot workflow that uses the Schwartz’ reagent and [(η3-1-tert-butylindenyl)(μ-Cl)Pd]2 as sensor generates a palladium complex displaying red-shifted CD inductions and characteristic UV changes. These chiroptical responses are accurately correlated to the enantiomeric ratio and total concentration, respectively, of the original nitrile. 
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  3. A reaction‐based optical relay sensing strategy that enables accurate determination of the concentration and enantiomeric ratio (er) of challenging chiral alcohols exhibiting stereocenters at the α‐, β‐, γ‐ or even δ‐position or hard‐to‐detect cryptochirality arising from H/D substitution is described. This unmatched application scope is achieved with a conceptually new sensing approach by which the alcohol moiety is replaced with an optimized achiral sulfonamide chromophore to minimize the distance between the covalently attached chiroptical reporter unit and the stereogenic center in the substrate. The result is a remarkably strong, red‐shifted CD induction that increases linearly with the sampleer. The CD sensing part of the tandem assay is seamlessly coupled to a redox reaction with a quinone molecule to generate a characteristic UV response that is independent of the enantiopurity of the alcohol and thus allows determination of the total analyte concentration. The robustness and utility of the CD/UV relay are further verified by chromatography‐free asymmetric reaction analysis with small aliquots of crude product mixtures, paving the way toward high‐throughput chiral compound screening workflows which is a highly sought‐after goal in the pharmaceutical industry. 
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  4. We report the discovery of an extremely high-velocity outflow (EHVO) in the most luminous QSO (LBol∼ 2.29 × 1048erg/s), named SMSS J2157-3602, atz = 4.692. Combined XSHOOTER and NIRES observations reveal that the EHVO reaches a maximum velocity ofvmax ∼ 0.13cand persists over rest-frame timescales of a few months up to one year. SMSS J2157-3602 also exhibits one of the highest balnicity index values discovered for an EHVO so far. In addition, the blueshifted CIV emission traces a high-velocity (vCIV50∼ 4660 km/s) outflow from the broad-line region (BLR). Thanks to an XMM-Newton observation, we were also able to reveal the X-ray weak nature of this QSO, which likely prevents the overionization of the innermost disk atmosphere and facilitates the efficient launch of the detected EHVO and BLR winds. The extraordinary luminosity of SMSS J2157-3602 and the extreme velocity of the EHVO make it a unique laboratory for testing active galactic nucleus (AGN) driven feedback under extreme conditions. Current uncertainties on the outflow’s location and column density strengthen the case for a dedicated follow-up, which will be essential to assess the full feedback potential of this remarkable quasar. 
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  5. Isatins are extensively researched compounds with diverse applications, particularly as synthetic precursors in pharmaceutical developments. However, their use as optical probes for enantioselective sensing of chiral amines has not been explored to date. Herein, we present a novel chiroptical assay with an optimized isatin that generates strong, red‐shifted circular dichroism (CD) signals at approximately 380 nm upon ketimine formation with chiral amines. The intensity of the induced CD signal increases linearly with the enantiomeric excess of the analyte and thus allows quantitative chirality analysis. The general usefulness of this approach is demonstrated with a broad range of aliphatic and aromatic chiral amines, and by accurate determination of the enantiomeric composition of 10 samples. 
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  6. We ask how fiscal deficits are financed in environments with two key features: (i) nominal rigidity, and (ii) a violation of Ricardian equivalence due to finite lives or liquidity constraints. In such environments, deficits can contribute to their own financing through two channels: a boom in real economic activity, which expands the tax base; and a surge in inflation, which erodes the real value of nominal government debt. Our main theoretical result establishes that this mechanism becomes more potent as fiscal adjustment is delayed, leading to full self‐financing in the limit: if the monetary authority does not lean too heavily against the fiscal stimulus, then the government can run a deficit today, refrain from tax hikes or spending cuts in the future, and still see its debt converge back to its initial level. We further demonstrate that a significant degree of self‐financing is achievable when the theory is disciplined by empirical evidence on marginal propensities to consume, nominal rigidities, the monetary policy reaction, and the speed of fiscal adjustment. 
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  7. Jha, Sangita; Roychowdhury, Mrinal; Verma, Saurabh (Ed.)
    We present an introduction to the area of computability in dynamical systems. One of the central questions in this area is if relevant dynamical objects can be algorithmically presented by a Turing machine. After providing an overview of the relevant objects we discuss recent results concerning the computability of the entropy for symbolic systems and the computability of Julia sets as well as their Brolin–Lyubich measures. 
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  8. Piano stool complexes have been studied over many years and found widespread applications in organic synthesis, catalysis, materials and drug development. We now report the first examples of quantitative chiroptical molecular recognition of chiral compounds through click‐like η6-arene coordination with readily available half sandwich complexes. This conceptually new approach to chirality sensing is based on irreversible acetonitrile displacement of [Cp*Ru(CH3CN)3]PF6 by an aromatic target molecule, a process that is fast and complete within a few minutes at room temperature. The metal coordination coincides with characteristic circular dichroism inductions that can be easily correlated to the absolute configuration and enantiomeric ratio of the bound molecule. A relay assay that decouples the determination of the enantiomeric composition and of the total sample amount by a practical CD/UV measurement protocol was developed and successfully tested. The introduction of piano stool complexes to the chiroptical sensing realm is mechanistically unique and extends the scope of currently known methods with small‐molecule probes that require the presence of amino, alcohol, carboxylate or other privileged functional groups for binding of the target compound. A broad application range including pharmaceutically relevant multifunctional molecules and the use in chromatography‐free asymmetric reaction analysis are also demonstrated. 
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  9. The analysis of the absolute configuration, enantiomeric composition, and concentration of chiral compounds are frequently encountered tasks across the chemical and health sciences. Chiroptical sensing methods can streamline this work and allow high-throughput screening with remarkable reduction of operational time and cost. During the last few years, significant methodological advances with innovative chirality sensing systems, the use of computer-generated calibration curves, machine learning assistance, and chemometric data processing, to name a few, have emerged and are now matched with commercially available multi-well plate CD readers. These developments have reframed the chirality sensing space and provide new opportunities that are of interest to a large group of chemists. This review will discuss chirality sensing strategies and applications with representative small-molecule CD sensors. Emphasis will be given to important milestones and recent advances that accelerate chiral compound analysis by outperforming traditional methods, conquer new directions, and pioneering efforts that lie at the forefront of chiroptical high-throughput screening developments. The goal is to provide the reader with a thorough understanding of the current state and a perspective of future directions of this rapidly emerging field. 
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