An Abnormal N‐Heterocyclic Carbene–Carbon Dioxide Adduct from Imidazolium Acetate Ionic Liquids: The Importance of Basicity

In the reaction of 1‐ethyl‐3‐methylimidazolium acetate [C₂C₁Im][OAc] ionic liquid with carbon dioxide at 125 °C and 10 MPa, not only the known N‐heterocyclic carbene (NHC)–CO₂ adduct I , but also isomeric aNHC‐CO₂ adducts II and III were obtained. The abnormal NHC‐CO₂ adducts are stabilized by the presence of the polarizing basic acetate anion, according to static DFT calculations and ab initio molecular dynamics studies. A further possible reaction pathway is facilitated by the high basicity of the system, deprotonating the initially formed NHC‐CO₂ adduct I , which can then be converted in the presence of the excess of CO₂ to the more stable 2‐deprotonated anionic abnormal NHC–CO₂ adduct via the anionic imidazolium‐2,4‐dicarboxylate according to DFT calculations on model compounds. This suggests a generalizable pathway to abnormal NHC complex formation.     

GC analysis of gas in halogen lamps using a new sampling device

Summary A new type of gas sampling device was constructed to improve the analysis of the gas in halogen lamps. Low levels of gases such as O₂, CH₄, C₂H₄ and CH₃Br could be determined by the techniques worked out.     

Q value related mass determinations using a Penning trap

We report here about measurements of reaction and decay Q values by precise determination of pairs of atomic masses. These were performed with the Penning trap mass spectrometer SMILETRAP. Measurements with Penning traps give reliable and accurate masses, in particular Q values, due to the fact that certain systematic errors to a great deal cancel in the mass difference between the two atoms defining the Q value. Some Q values that are of fundamental interest will be discussed here, for example, a new Q value for the ⁶Li (n,γ) ⁷Li reaction, for the β-decay of tritium, related to properties of the electron neutrino mass, and for the neutrino-less double β-decay of ⁷⁶Ge, related to the question of whether the neutrino is a Majorana particle or not. In case of the latter two we report the most accurate Q values, namely 18,589.8(12) eV for the tritium decay and 2,038.997(46) keV for the neutrino-less double β-decay of ⁷⁶Ge.     

Influence of the activation temperature on structural and textural properties of NiMo/Al2O3 hydrodesulfurization catalysts

Investigations of a commercial NiMo/Al₂O₃ hydrodesulfurization (HDS) catalyst are directed towards optimization of the activation procedure of HDS catalyst concerning active phase formation and thermal stability. Structural and textural data obtained with XRD, IR-FTIR, XPS and LTNA reveal that the optimal temperature for the formation of active species on the catalyst surface and an appropriate pore structure is 300°C.     

Steepest Descent, CG, and Iterative Regularization of Ill-Posed Problems

The state of the art iterative method for solving large linear systems is the conjugate gradient (CG) algorithm. Theoretical convergence analysis suggests that CG converges more rapidly than steepest descent. This paper argues that steepest descent may be an attractive alternative to CG when solving linear systems arising from the discretization of ill-posed problems. Specifically, it is shown that, for ill-posed problems, steepest descent has a more stable convergence behavior than CG, which may be explained by the fact that the filter factors for steepest descent behave much less erratically than those for CG. Moreover, it is shown that, with proper preconditioning, the convergence rate of steepest descent is competitive with that of CG.This revised version was published online in October 2005 with corrections to the Cover Date.     

Solution-phase parallel synthesis of a pyridinium pyrazol-3-olate inner salt library using a three-component reaction

We present here the discovery of a novel, versatile, multicomponent reaction leading to various 4-[4-(pyridinium-1-yl)-2,5-dioxo-2,5-dihydro-1H-pyrrol-3-yl]-2H-pyrazol-3-olate inner salts. The structure of the unusual zwitterionic inner salts was elucidated, and the scope of the novel reaction was investigated. After rapid optimization, the reaction was adapted to parallel synthesis, and an 800-membered compound library was produced.     

The Campbell- Hausdorff Series of Local Analytic Bruck Loops

The class of local analyitic Bruck loops (or equivalently K-loops) is strongly related to locally symmetric spaces. In particular, both have Lie triple systems as their tangent algebra. In this paper, we consider the existence and some properties of the Campbell-Hausdorff series of local analytic Bruck loops (K-loops). This formula can be used to determine the local symmetries of the associated symmetric space.     

Robust regression for mixed Poisson–Gaussian model

This paper focuses on efficient computational approaches to compute approximate solutions of a linear inverse problem that is contaminated with mixed Poisson–Gaussian noise, and when there are additional outliers in the measured data. The Poisson–Gaussian noise leads to a weighted minimization problem, with solution-dependent weights. To address outliers, the standard least squares fit-to-data metric is replaced by the Talwar robust regression function. Convexity, regularization parameter selection schemes, and incorporation of non-negative constraints are investigated. A projected Newton algorithm is used to solve the resulting constrained optimization problem, and a preconditioner is proposed to accelerate conjugate gradient Hessian solves. Numerical experiments on problems from image deblurring illustrate the effectiveness of the methods.     

A combined approach of differential scanning calorimetry and hot-stage microscopy with image analysis in the investigation of sulfathiazole polymorphism

A combination of differential scanning calorimetry and hot-stage microscopy with image analysis has been used to investigate the polymorphism of sulfathiazole. The use of light intensity profiles obtained from the HSM images, as an alternative way to present results of the HSM analysis, was found to be useful in describing and verifying thermal events. The approach provides a unique insight into the polymorphic transformations and thermal behaviour exhibited by this compound. The results of the experiments show that sulfathiazole tends to crystallise as mixtures of polymorphs, even though the literature methods for producing pure polymorph were followed.