Impact of APCI ionization source in liquid chromatography tandem mass spectrometry based tissue distribution studies

Measurement of test article concentration in tissue samples has been an important part of pharmacokinetic study and has helped to co‐relate pharmacokinetic/pharmacodynamic relationships since the 1950s. Bioanalysis of tissue samples using LC–MS/MS comes with unique challenges in terms of sample handling and inconsistent analyte response owing to nonvolatile matrix components. Matrix effect is a phenomenon where the target analyte response is either suppressed or enhanced in the presence of matrix components. Based on previous reports electrospray ionization (ESI) mode of ionization is believed to be more affected by matrix components than atmospheric pressure chemical ionization (APCI) or atmospheric pressure photoionization. To explore the impact of ionization source with respect to bioanalysis of tissue samples, five structurally diverse compounds – atenolol, verapamil, diclofenac, propranolol and flufenamic acid – were selected. Quality control standards were spiked into 10 different biological matrices like whole blood, liver, heart, brain, spleen, kidney, skeletal muscle, eye and skin tissue and were quantified against calibration standards prepared in rat plasma. Quantitative bioanalysis was performed utilizing both APCI and ESI mode and results were compared. Quality control standards when analyzed with APCI mode were found to be more consistent in terms of accuracy and precision as compared with ESI mode. Additionally, for some instances, up to 20‐fold broader dynamic linearity range was observed with APCI mode as compared with ESI mode. As phospholid interferences have poor response in APCI mode, protein precipitation extraction technique can be used for multimatrix quantitation, which is more amenable to automation. The approach of multiple biological matrix quantitation against a single calibration curve helps bioanalysts to reduce turnaround time. Copyright © 2016 John Wiley & Sons, Ltd.     

Efficient Piezoelectric Energy Harvesting from a Discrete Hybrid Bismuth Bromide Ferroelectric Templated by Phosphonium Cation

Bismuth containing hybrid molecular ferroelectrics are receiving tremendous attention in recent years owing to their stable and non-toxic composition. However, these perovskite-like structures are primarily limited to ammonium cations. Herein, we report a new phosphonium based discrete perovskite-like hybrid ferroelectric with a formula [Me(Ph)₃P]₃[Bi₂Br₉] ( MTPBB ) and its mechanical energy harvesting capability. The Polarization-Electric field (P-E) measurements resulted in a well-defined ferroelectric hysteresis loop with a remnant polarization value of 2.1 μC cm⁻². Piezoresponse force microscopy experiments enabled visualization of the ferroelectric domain structure and evaluation of the piezoelectric strain coefficient (d₃₃) for an MTPBB single crystal and thin film sample. Furthermore, flexible devices incorporating MTPBB in polydimethylsiloxane (PDMS) matrix at various concentrations were fabricated and explored for their mechanical energy harvesting properties. The champion device with 20 wt % of MTPBB in PDMS rendered a maximum peak-to-peak open-circuit voltage of 22.9 V and a maximum power density of 7 μW cm⁻² at an optimal load of 4 MΩ. Moreover, the potential of MTPBB -based devices in low power electronics was demonstrated by storing the harvested energy in various electrolytic capacitors.     

Large-scale concept ontology for multimedia

As increasingly powerful techniques emerge for machine tagging multimedia content, it becomes ever more important to standardize the underlying vocabularies. Doing so provides interoperability and lets the multimedia community focus ongoing research on a well-defined set of semantics. This paper describes a collaborative effort of multimedia researchers, library scientists, and end users to develop a large standardized taxonomy for describing broadcast news video. The large-scale concept ontology for multimedia (LSCOM) is the first of its kind designed to simultaneously optimize utility to facilitate end-user access, cover a large semantic space, make automated extraction feasible, and increase observability in diverse broadcast news video data sets.     

Domain-Size-Dependent Residual Stress Governs the Phase-Transition and Photoluminescence Behavior of Methylammonium Lead Iodide

Methylammonium lead iodide (MAPbI₃) perovskite has garnered significant interest as a versatile material for optoelectronic applications. The temperature-dependent photoluminescence (TDPL) and phase-transition behaviors revealed in previous studies have become standard indicators of defects, stability, charge carrier dynamics, and device performance. However, published reports abound with examples of irregular photoluminescence and phase-transition phenomena that are difficult to reconcile, posing major challenges in the correlation of those properties with the actual material state or with the subsequent device performance. In this paper, a unifying explanation for the seemingly inconsistent TDPL and phase-transition (orthorhombic-to-tetragonal) characteristics observed for MAPbI₃ is presented. By investigating MAPbI₃ perovskites with varying crystalline states, ranging from polycrystal to highly oriented crystal as well as single-crystals, key features in the TDPL and phase-transition behaviors are identified that are related to the extent of crystal domain-size-dependent residual stress and stem from the considerable volume difference (ΔV ≈ 4.5%) between the primitive unit cells of the orthorhombic (at 80 K) and tetragonal phases (at 300 K) of MAPbI₃. This fundamental connection is essential for understanding the photophysics and material processing of soft perovskites.     

Validation of the GROMOS 54A7 Force Field Regarding Mixed α/β‐Peptide Molecules

A molecular‐dynamics (MD) simulation study of two heptapeptides containing α‐ and β‐amino acid residues is presented. According to NMR experiments, the two peptides differ in dominant fold when solvated in MeOH: peptide 3 adopts predominantly β‐hairpin‐like conformations, while peptide 8 adopts a 14/15‐helical fold. The MD simulations largely reproduce the experimental data. Application of NOE atom? atom distance restraining improves the agreement with experimental data, but reduces the conformational sampling. Peptide 3 shows a variety of conformations, while still agreeing with the NOE and ³J‐coupling data, whereas the conformational ensemble of peptide 8 is dominated by one helical conformation. The results confirm the suitability of the GROMOS 54A7 force field for simulation or structure refinement of mixed α/β‐peptides in MeOH.     

Stochastic P-bifurcation in a nonlinear impact oscillator with soft barrier under Ornstein–Uhlenbeck process

Nonlinear Dynamics - This study investigates the effect of randomness in the forcing on a harmonically excited bilinear impact oscillator with a soft barrier. The system parameter range considered...