Continuous Flow Synthesis of Metal–NHC Complexes**

The use of weak bases and mild conditions is currently the most sustainable and attractive synthetic approach for the preparation of late-transition metal complexes, some of which are widely used in catalysis, medicinal chemistry and materials science. Herein, the use of cuprate, aurate or palladate species for a continuous flow preparation of Cu^I, Au^I and Pd^II-NHC complexes is reported. All reactions examined proceed under extremely mild conditions and make use of technical grade acetone as solvent. The scalability of the process was exemplified in a multigram-scale synthesis of [Cu(IPr)Cl].     

Molecular weight distribution in emulsion polymerization. I. The homopolymer case

A model for evaluating the instantaneous degree of polymerization distribution of homopolymers produced in emulsion, based on the mathematics of the Markov chains, is developed. The model accounts for any number of active chains per particle, as well as for the two fundamental mechanisms of chain termination: mono- and bi-molecular, both by combination and by disproportionation. The core of the model is the so called subprocessmain process treatment, which allows us to correctly evaluate the degree of polymerization of the chains growing in the polymer particles, by distinguishing between the events experienced by the polymer chain which imply a change of its degree of polymerization (subject transitions) and those which imply only a change in the particle state (environment transitions). This is obtained by properly defining the one-step transition probability matrix of the relevant Markov process. Once this is done, the evaluation of the distribution of the degrees of polymerization reduces to a few simple operations among matrices. Explicit expressions for the instantaneous probability density functions and the relative cumulative distributions are obtained. The application of such relationships is facilitated by the numerical procedures reported in the Appendices. The results of the model developed in this work are in agreement with those of earlier models in the range of parameter values of practical interest. In the limit of very low molecular weights, only the model developed in this work provides the correct answer. Moreover, a much more significant result is its applicability to the case of emulsion copolymerization, as it is shown in Part II.     

An Evaluation of Entropy Measures for Microphone Identification

Research findings have shown that microphones can be uniquely identified by audio recordings since physical features of the microphone components leave repeatable and distinguishable traces on the audio stream. This property can be exploited in security applications to perform the identification of a mobile phone through the built-in microphone. The problem is to determine an accurate but also efficient representation of the physical characteristics, which is not known a priori. Usually there is a trade-off between the identification accuracy and the time requested to perform the classification. Various approaches have been used in literature to deal with it, ranging from the application of handcrafted statistical features to the recent application of deep learning techniques. This paper evaluates the application of different entropy measures (Shannon Entropy, Permutation Entropy, Dispersion Entropy, Approximate Entropy, Sample Entropy, and Fuzzy Entropy) and their suitability for microphone classification. The analysis is validated against an experimental dataset of built-in microphones of 34 mobile phones, stimulated by three different audio signals. The findings show that selected entropy measures can provide a very high identification accuracy in comparison to other statistical features and that they can be robust against the presence of noise. This paper performs an extensive analysis based on filter features selection methods to identify the most discriminating entropy measures and the related hyper-parameters (e.g., embedding dimension). Results on the trade-off between accuracy and classification time are also presented.     

Competition in the carrier capture between InGaAs/AlGaAs quantum dots and deep point defects

The presence of an extrinsic photoluminescence (PL) band peaked at 1.356 eV at low temperature is observed, on a large number of self-assembled InAs and In_0.5Ga_0.5As quantum dot (QD) structures, when exciting just below the GaAs absorption edge. A detailed optical characterization allows us to attribute the 1.356 eV PL band to the radiative transition between the conduction band and the doubly ionized Cu _Ga acceptor in GaAs. A striking common feature is observed in all investigated samples, namely a resonant quenching of the QD-PL when exciting on the excited level of this deep defect. Moreover, the photoluminescence excitation (PLE) spectrum of the 1.356 eV emission turns out to be almost specular to the QD PLE. This correlation between the PL efficiency of the QDs and the Cu centers evidences a competition in the carrier capture arising from a resonant coupling between the excited level of the defect and the electronic states of the wetting layer on which the QDs nucleate. The estimated Cu concentration is compatible with a contamination during the epitaxial growth. Received 13 November 2001 / Received in final form 28 May 2002 Published online 19 July 2002     

Luminescence of CsPbBr3-like quantum dots in CsBr single crystals

Luminescence and decay kinetics of the Pb²⁺ aggregates in CsBr host crystals were measured in the 4–300 K temperature interval and in 10⁻¹⁰–10⁻³ time scale. Their emission properties are similar to those of CsPbBr₃ bulk crystal showing a subnanosecond free exciton emission in the 520–540 nm spectral region and slower trapped exciton emission in the 530–580 nm spectral region. An efficient energy exchange between the free and trapped exciton states is shown by the temperature dependencies of emission spectra. The quantum size effect is demonstrated in the high energy shift and broadening of the absorption and emission spectra and an estimate of the size of the CsPbBr₃-like aggregates is provided. Independent evidence of the presence of the CsPbBr₃ and Cs₄PbBr₆ aggregated phases in the CsBr host was obtained by X-ray structural studies.     

Study of post-growth annealing and Ga coverage effects in low-density GaAs/AlGaAs quantum dots grown by modified droplet epitaxy

We present a detailed analysis of the Ga coverage and of the post-growth annealing effects on the optical properties of very-low-density self-assembled GaAs/AlGaAs quantum dots grown by modified droplet epitaxy. Through theoretical calculation of the QD electronic states, including thermally activated Al–Ga interdiffusion processes, we were able to relate our spectroscopic observations to QD structural properties.     

Digital twin of a combustion furnace operating in flameless conditions: reduced-order model development from CFD simulations

The present paper presents the first-of-its-kind digital twin for a furnace operating in flameless combustion conditions. A methodology combining data compression, by means of Proper Orthogonal Decomposition (POD), and interpolation, using Kriging, was developed to design physics-based, reduced-order models (ROMs) for the prediction of combustion data at unexplored operating conditions. Three-dimensional simulations with detailed chemistry were carried out, spanning a wide range of operating conditions in terms of fuel composition (methane-hydrogen mixtures from pure methane to pure hydrogen), equivalence ratio (from 0.7 to 1) and air injector diameter (to adjust the air jet entrainment). Based on the available simulations, a ROM was developed, to predict both spatial fields, local and integral values of thermochemical variables at working conditions not included in the ROM development. Results showed that the developed ROM could reliably predict the temperature and main chemical species distribution in the furnace with an overall error below 10%, proving the effectiveness of the approach for the development of digital twins of combustion systems. A remarkable accuracy was observed for the prediction of specific quantities, including wall temperatures, OH decay length, OH peak value and location and exhaust gas composition, including pollutants, with prediction errors always below 5%, showing the potential of the approach to develop soft sensors.     

Synthetic Access to Aromatic α-Haloketones

α-Haloketones play an essential role in the synthesis of complex N-, S-, O-heterocycles; of which some exhibit a remarkable biological activity. Research further illustrated that α-bromo-, α-chloro-, and α-iodoketones are key precursors for blockbuster pharmacological compounds. Over the past twenty years, substantial advances have been made in the synthesis of these industrially relevant building blocks. Efforts have focused on rendering the synthetic protocols greener, more effective and versatile. In this survey, we summarised and thoroughly evaluated the progress of the field, established in the past two decades, in terms of generality, efficacy and sustainability.