Shrinking droplets in electrospray ionization and their influence on chemical equilibria

We investigated how chemical equilibria are affected by the electrospray process, using simultaneous in situ measurements by laser-induced fluorescence (LIF) and phase Doppler anemometry (PDA). The motivation for this study was the increasing number of publications in which electrospray ionization mass spectrometry is used for binding constant determination. The PDA was used to monitor droplet size and velocity, whereas LIF was used to monitor fluorescent analytes within the electrospray droplets. Using acetonitrile as solvent, we found an average initial droplet diameter of 10 microm in the electrospray. The PDA allowed us to follow the evolution of these droplets down to a size of 1 microm. Rhodamine B-sulfonylchloride was used as a fluorescent analyte within the electrospray. By spatially resolved LIF it was possible to probe the dimerization equilibrium of this dye. Measurements at different spray positions showed no influence of the decreasing droplet size on the monomer-dimer equilibrium. However, with the fluorescent dye pair DCM and oxazine 1 it was shown that a concentration increase does occur within electrosprayed droplets, using fluorescence resonance energy transfer as a probe for the average pair distance.     

Explainable AI: A Review of Machine Learning Interpretability Methods

Recent advances in artificial intelligence (AI) have led to its widespread industrial adoption, with machine learning systems demonstrating superhuman performance in a significant number of tasks. However, this surge in performance, has often been achieved through increased model complexity, turning such systems into “black box” approaches and causing uncertainty regarding the way they operate and, ultimately, the way that they come to decisions. This ambiguity has made it problematic for machine learning systems to be adopted in sensitive yet critical domains, where their value could be immense, such as healthcare. As a result, scientific interest in the field of Explainable Artificial Intelligence (XAI), a field that is concerned with the development of new methods that explain and interpret machine learning models, has been tremendously reignited over recent years. This study focuses on machine learning interpretability methods; more specifically, a literature review and taxonomy of these methods are presented, as well as links to their programming implementations, in the hope that this survey would serve as a reference point for both theorists and practitioners.     

A fully validated method for the determination of lacosamide in human plasma using gas chromatography with mass spectrometry: Application for therapeutic drug monitoring

A simple gas chromatographic method with mass spectrometry detection was developed and validated for the determination of lacosamide in human plasma. Lacosamide and the internal standard, levetiracetam‐d₆, were extracted from 200 μL plasma, by a solid‐phase extraction through HF Bond Elut C₁₈ columns, and derivatized using N‐methyl‐N‐tert‐butyldimethylsilyltrifluoroacetamide with 1% tert‐butyldimethylsilylchloride in acetonitrile. The limit of quantification was found to be 0.20 μg/mL and the assay was linear up to 20.0 μg/mL with correlation coefficient ≥0.994. The intra‐ and interday precision values were <4.1% in terms of relative standard deviation (%) and the values of intra‐ and interday accuracy were found to be within –7.2 and 5.3% in terms of relative error (%). Absolute recovery of the method for lacosamide was determined at three concentration levels and ranged from 92.5 to 97.6%. The developed method uses small volumes of plasma and proved to be simple, rapid, and sensitive for the determination of lacosamide in plasma. This method can be used in routine every day analysis of plasma samples obtained from patients who follow respective antiepileptic treatment and for the investigation of clinical and forensic cases where lacosamide is involved.     

Palladium embedded in SnO2 enhances the sensitivity of flame-made chemoresistive gas sensors

Microchimica Acta - This review (with 187 refs.) summarizes the progress that has been made in the design of lateral flow biosensors (LFBs) based on the use of micro- and nano-materials. Following...     

Technical challenges in tackling regulatory concerns for urban atmospheric nanoparticles

Recent Euro 5 and Euro 6 vehicle emission standards are the first ever initiative to control particles on a number basis at the source. Related standards are also desirable for ambient nanoparticles (taken in this article to be those below 300 nm) to protect against possible adverse effects on public health and the environment. However, there are a number of technical challenges that need to be tackled before developing a regulatory framework for atmospheric nanoparticles. Some of the challenges derive from a lack of standardisation of the key measurement parameters, including sampling, necessary for robust evaluation of particle number concentrations, especially in the context of insufficient knowledge of the physicochemical characteristics of emerging sources (i.e. bio-fuel derived and manufactured nanoparticles). Ideally, ambient concentrations of primary particles could be linked to primary particle emissions by use of nanoparticle dispersion models, and secondary nanoparticles using photochemical modeling tools. The limitations in these areas are discussed. Although there is inadequate information on the exact biological mechanism through which these particles cause harm, it is argued that this should not in itself delay the introduction of regulation. This article reviews the missing links between the existing knowledge of nanoparticle number concentrations and the advances required to tackle the technical challenges implied in developing regulations.     

Flexible,Multifunctional, Magnetically Actuated Nanocomposite Films

Filler nanoparticles greatly enhance the performance of polymers and minimize filler content in the resulting nanocomposites. At the same time, they challenge the manufacturing of such nanocomposites by filler agglomeration and non‐uniform spatial distribution. Here, multifunctional nanocomposite films are made by capitalizing on flame‐synthesis of ceramic or metal filler nanoparticles followed by rapid, in situ deposition on sacrificial substrates, resulting in a filler film with controlled porosity. The polymer is then spin‐coated on the porous film that retained its stochastic but uniform structure, resulting in nanocomposites with homogeneous filler distribution and high filler‐loading. By sequential repetition of this procedure, sophisticated, multilayer, free‐standing, plasmonic‐ (Ag‐Fe₂O₃) and phosphorescent‐superparamagnetic (Y₂O₃:Eu³⁺‐ Fe₂O₃) actuators are made by precisely tuning the polymer thickness between each functional nanostructured layer. These actuators are quite flexible, have fast response times, and exhibit superior superparamagnetism due to their high filler content and homogeneous spatial distribution.     

Photostabilization of oxolinic acid in hydroxypropyl-β-cyclodextrins; implications for the effect of molecular self-assembly phenomena

Oxolinic acid (OXA) is a first-generation quinolone antibacterial agent, known to cause drug induced photosensitivity. In the present work its photoinduced degradation was monitored under simulated solar irradiation. The effect of photoprotecting agents on OXA stability was also assessed by drug complexation with hydroxypropyl-β-cyclodextrin (HPβCD). The complex was studied by UV-Vis and ¹H (2D) NMR Spectroscopy. A photostability indicating chromatographic method was developed and validated. Because OXA is insoluble in acidic solutions, and because an acidic solvent is necessary for successful chromatographic separation, a procedure was developed to pre-treat the sample. This method is suitable for the separation of degradation products from OXA and from each other. The method was also evaluated in the presence of HPβCD, in order to ensure that inclusion complexation did not generate inaccuracies. Investigation of OXA photodegradation profiles confirms first order kinetics and acceleration at higher initial sample concentrations. A 94% photostabilization upon complexation with HPβCD was achieved. Furthermore, molecular self association phenomena were determined by self titration experiments, using ¹H NMR Spectroscopy and suggestions were made for the photostabilization mechanism of cyclodextrins.     

Some Parameterized Quantum Midpoint and Quantum Trapezoid Type Inequalities for Convex Functions with Applications

Quantum information theory, an interdisciplinary field that includes computer science, information theory, philosophy, cryptography, and entropy, has various applications for quantum calculus. Inequalities and entropy functions have a strong association with convex functions. In this study, we prove quantum midpoint type inequalities, quantum trapezoidal type inequalities, and the quantum Simpson’s type inequality for differentiable convex functions using a new parameterized q-integral equality. The newly formed inequalities are also proven to be generalizations of previously existing inequities. Finally, using the newly established inequalities, we present some applications for quadrature formulas.     

The periodic table of urea derivative: small molecules of zinc(II) and nickel(II) of diverse antimicrobial and antiproliferative applications

Molecular Diversity - Two complexes of Zn(II) and Ni(II) ions with the urea derivative, 2-benzimidazolyl-urea (BZIMU), of formulae [ZnBZIMU)2(H2O)](NO3)2 (1) and [Ni(BZIMU)2(CH3CH2OH)2](NO3)2 (2)...     

Potential energy surfaces of carbon dioxide

Several bent valence states of CO₂ are characterized by means of full-valence-space MCSCF calculations. The ground state potential energy surface exhibits a double well corresponding to a ring minimum, with C_2vsymmetry (¹A₁) and a 73.1° OCO angle, in addition to the linear (¹σ) global minimum. The transition state for the ring opening process, which has a barrier of 12.1 kcal/mole with respect to the ring minimum, is however found to have C_s symmetry. Double minima are also shown to exist for the ¹A₂, ¹B₁ and ¹B₂ excited states. However, in these cases all minima are bent. Cross sections through the ground state potential energy surface corresponding to the two collinear exchange reactions O(¹D) + CO(¹σ⁺) → OC(¹σ⁺) + O(¹D) C(³P) + O₂(³σ) → CO(¹σ⁺) + O(¹D) are also calculated and their energy contour maps are reported. The latter reveals the existence of a stable linear intermediate with the structure COO. © 1994 John Wiley & Sons, Inc.