Present state-of-the-art in exponential fitting. A contribution dedicated to Liviu Ixaru on his 70th birthday

The standard monograph in this area is the book Exponential fitting by Ixaru and Vanden Berghe (Kluwer, Boston - Dordrecht - London, 2004) but a fresh look on things is necessary because many new contributions have been accumulated in the meantime. With no claim that our investigation is exhaustive we consider various directions of interest, try to integrate the new contributions in a natural, easy to follow way, and also detect some open problems of acute interest.     

Quantification of cadmium and lead in offal by SF-ICP-MS: Method development and uncertainty estimate

Offal of bovine, ovine and porcine are able to accumulate potentially toxic heavy metals, such as Cd and Pb, posing a risk for human health. For this reason, the Commission Regulation no. 466/2001 provided the maximum admitted levels for these metals in this kind of matrix (Cd, 500 ng g⁻¹ in all kinds of offal; Pb, 500 ng g⁻¹ in liver and 1000 ng g⁻¹ in kidney). A method based on sector field inductively coupled plasma mass spectrometry for Cd and Pb quantification in calf liver was developed and further applied to offal of different animals. The uncertainty of measurements was calculated according to the Eurachem/Citac Guide. The method LoDs and LoQs were 3.5 and 11 ng g⁻¹ for Cd, and 2.0 and 6.0 ng g⁻¹ for Pb. The repeatability and the intra-laboratory reproducibility showed relative standard deviations equal to 2.25% and 1.99% for Cd and 1.49% and 6.55% for Pb. Relative expanded uncertainties at the mean value in calf liver were 4.74% for Cd and 13.8% for Pb. In Italian offal the following concentration intervals were found (in ng g⁻¹): (i) Cd: calf, from <3.5 in spleen and lung to 96.4 in kidney; lamb, <3.5 in all offal; pig, 114 in liver and (ii) Pb: calf, from 4.03 in lung to 31.8 in liver; lamb, from 4.71 in heart to 279 in liver; pig, 9.19 in liver.     

Recent Developments in the Application of Phosphorescent Iridium(III) Complex Systems

The recent developments in using iridium(III) complexes as phosphorescent emitters in electroluminescent devices, such as (white) organic light‐emitting diodes and light‐emitting electrochemical cells, are discussed. Additionally, applications in the emerging fields of molecular sensors, biolabeling, and photocatalysis are briefly evaluated. The basic strategies towards charged and non‐charged iridium(III) complexes are summarized, and a wide range of assemblies is discussed. Small‐molecule‐ and polymer‐based materials are under intense investigation as emissive systems in electroluminescent devices, and special emphasis is placed on the latter with respect to synthesis, characterization, electro‐optical properties, processing technologies, and performance.     

Sustainable Root Zone Salinity and Shallow Water Table in the Context of Land Retirement

This study uses five years of field data from the Land Retirement Demonstration Project located in western Fresno County of California to develop a comprehensive theoretical and numerical modeling framework to evaluate the specific site conditions required for a sustainable land retirement outcome based on natural drainage. Using field data, principles of mass balance in a control volume, the HYDRUS-1D software package for simulating one-dimensional movement of water, heat, and multiple solutes in variably-saturated media, and a model-independent parameter optimizer, the processes of soil water and solute movement in root zone and deep vadose zone were investigated. The optimization of unsaturated soil hydraulic parameters and downward flux (natural drainage) from the control volume against observed vadose zone salinity levels and shallow groundwater levels yield difficult to obtain natural drainage rate as a function of water table height within the control volume. The results show that the unsaturated soil hydraulic properties and the downward flux from the soil profile are the critical parameters. A “natural drainage approach” to sustainable land management for drainage-impaired land is proposed. With this approach it is feasible to design a sustainable land use regimen for drainage-impaired lands in general and retired lands in particular.     

Microscopic Determination of Carrier Density and Mobility in Working Organic Electrochemical Transistors

A comprehensive understanding of electrochemical and physical phenomena originating the response of electrolyte‐gated transistors is crucial for improved handling and design of these devices. However, the lack of suitable tools for direct investigation of microscale effects has hindered the possibility to bridge the gap between experiments and theoretical models. In this contribution, a scanning probe setup is used to explore the operation mechanisms of organic electrochemical transistors by probing the local electrochemical potential of the organic film composing the device channel. Moreover, an interpretative model is developed in order to highlight the meaning of electrochemical doping and to show how the experimental data can give direct access to fundamental device parameters, such as local charge carrier concentration and mobility. This approach is versatile and provides insight into the organic semiconductor/electrolyte interface and useful information for materials characterization, device scaling, and sensing optimization.     

Substrate Selection for Full Exploitation of Organic Semiconductor Films: Epitaxial Rubrene on β‐Alanine Single Crystals

Rubrene (RUB) is one of the most studied organic semiconductors because, in the orthorhombic single‐crystal phase, it exhibits a record exciton diffusion length and one of the highest charge carrier mobilities ever reported. Here, thin films of oriented crystalline RUB are successfully grown in vacuum on millimeter‐sized (010)‐β‐alanine (β‐ala) single crystals with a step‐growth protocol, exploiting organic epitaxy. The experimental characterization demonstrates that these RUB films grow in the orthorhombic polymorph with the (100)_RUB plane in contact with the (010)_β‐ala surface and with precise azimuthal orientations. A complementary study of the RUB(100)/β‐ala(010) interface, performed by computational simulations, confirms the epitaxial relations expected by considering the molecular scale corrugations of the surfaces. Moreover, thanks to the wide transparency region of β‐ala, the RUB absorption bands in the UV range are directly detected for the first time. Finally, removal of the water‐soluble substrate enables the integration of the films in field effect transistors as high quality active organic layers. The characteristics of such RUB‐based devices confirm the quality and versatility of epitaxial thin films for use in organic electronics.