Uptake and release kinetics of 22 polar organic chemicals in the Chemcatcher passive sampler

The Chemcatcher passive sampler, which uses Empore? disks as sampling phase, is frequently used to monitor polar organic chemicals in river water and effluents. Uptake kinetics need to be quantified to calculate time-weighted average concentrations from Chemcatcher field deployments. Information on release kinetics is needed if performance reference compounds (PRCs) are used to quantify the influence of environmental conditions on the uptake. In a series of uptake and elimination experiments, we used Empore? SDB disks (poly(styrenedivinylbenzene) copolymer modified with sulfonic acid groups) as a sampling phase and 22 compounds with a logK _ow (octanol–water partitioning coefficient) range from ?2.6 to 3.8. Uptake experiments were conducted in river water or tap water and lasted up to 25 days. Only 1 of 22 compounds (sulfamethoxazole) approached equilibrium in the uptake trials. Other compounds showed continuing non-linear uptake, even after 25 days. All compounds could be released from SDB disks, and desorption was proportionally higher in disks loaded for shorter periods. Desorption showed two-phase characteristics, and desorption was proportionally higher for passively sorbed compounds compared to actively loaded compounds (active loading was performed by pulling spiked river water over SDB disks using vacuum). We hypothesise that the two-phase kinetics and better retention of actively loaded compounds—and compounds loaded for a longer period—may be caused by slow diffusion of chemicals within the polymer. As sorption and desorption did not show isotropic kinetics, it is not possible to develop robust PRCs for adsorbent material like SDB disks.     

Novel ‘Nano in Nano’ Composites for Sustained Drug Delivery: Biodegradable Nanoparticles Encapsulated into Nanofiber Non‐Wovens

Novel ‘nano in nano’ composites consisting of biodegradable polymer nanoparticles incorporated into polymer nanofibers may efficiently modulate drug delivery. This is shown here using a combination of model compound‐loaded biodegradable nanoparticles encapsulated in electrospun fibers. The dye coumarin 6 is used as model compound for a drug in order to simulate drug release from loaded poly(lactide‐co‐glycolide) nanoparticles. Dye release from the nanoparticles occurs immediately in aqueous solution. Dye‐loaded nanoparticles which are encapsulated by electrospun polymer nanofibers display a significantly retarded release.

     

SO-I: a surrogate model algorithm for expensive nonlinear integer programming problems including global optimization applications

This paper presents the surrogate model based algorithm SO-I for solving purely integer optimization problems that have computationally expensive black-box objective functions and that may have computationally expensive constraints. The algorithm was developed for solving global optimization problems, meaning that the relaxed optimization problems have many local optima. However, the method is also shown to perform well on many local optimization problems, and problems with linear objective functions. The performance of SO-I, a genetic algorithm, Nonsmooth Optimization by Mesh Adaptive Direct Search (NOMAD), SO-MI (Müller et al. in Comput Oper Res 40(5):1383–1400, 2013), variable neighborhood search, and a version of SO-I that only uses a local search has been compared on 17 test problems from the literature, and on eight realizations of two application problems. One application problem relates to hydropower generation, and the other one to throughput maximization. The numerical results show that SO-I finds good solutions most efficiently. Moreover, as opposed to SO-MI, SO-I is able to find feasible points by employing a first optimization phase that aims at minimizing a constraint violation function. A feasible user-supplied point is not necessary.     

Spin-state dynamics of a photochromic iron(II) complex and its immobilization on oxide surfaces via phenol anchors

This work presents a detailed study of the photo-induced spin-state dynamics of the photochromic iron(II) complex 1, where the metal ion is in the field of a tripodal hexa-imine ligand with protolysable phenol groups. The nature of the complex’s ground state has been identified as a spin singlet by ¹H NMR and steady-state UV/vis spectroscopies, and its distorted octahedral structure was analyzed via crystal structure determination. Sub-picosecond and nanosecond time-resolved laser flash photolysis experiments identify the long-lived quintet state of 1 as the selective product of photoexcitation in the UV/vis spectral region. Thermal barriers of spin-state interconversion as a function of solvent and added base are derived from temperature-dependent rates of transient decay. Ground-state recovery is found to be significantly affected by the solvent and is strongly enhanced, in particular, by base-driven solvolysis of the ligand’s phenol groups. Partial spontaneous deprotonation of the phenolic hydroxyl groups of 1 seems to prevail on metal oxide surfaces, i.e. on alumina. Composite materials, like 1 at Al₂O₃, that retain the characteristic spectral features of the parent iron(II) complex can be readily obtained by wet impregnation of hydrous alumina with solutions of 1.     

Quasi-homogeneous hydrogenation with platinum and palladium nanoparticles stabilized by dendritic core-multishell architectures

Platinum and palladium nanoparticles, supported and stabilized by polymeric core-shell architectures, proved to be active catalysts for hydrogenation reactions. Here, two different reactions were used as probes to investigate the influence of the polymeric support: the hydrogenation of α-methyl styrene (AMS) to cumene and the partial hydrogenation of 1,5-cyclooctadiene (COD). We found that the stability of the nanoparticles and the rate of reaction are higher in the presence of a hydrophobic octadecyl shell within a three-shell polymer system. The kinetic study of AMS hydrogenation showed much higher activities for palladium nanoparticles than for platinum nanoparticles, and the obtained results (e.g., 35 kJ/mol for the activation energy) are of the same order of magnitude as reported earlier for palladium supported on alumina. A methanol/n-heptane biphasic mixture was tested for catalyst recycling and allowed for highly efficient catalyst separation with very low metal leaching.     

Ultrafast dynamics of isolated fluorenone

The ultrafast dynamics of isolated 9-fluorenone was studied by femtosecond time-resolved photoionization and photoelectron spectroscopy. The molecule was excited around 264-266 nm into the S(6) state. The experimental results indicate that the excitation is followed by a multistep deactivation. A time constant of 50 fs or less corresponds to a fast redistribution of energy within the initially excited manifold of states, i.e., a motion away from the Franck-Condon region. Internal conversion to the S(1) state then proceeds within 0.4 ps. The S(1) state is long-lived, and only a lower bound of 20 ps can be derived. In addition, we computed excited state energies and oscillator strengths by TD-DFT theory, supporting the interpretation of the experimental data.     

OH-stretch vibrational spectroscopy of hydroxymethyl hydroperoxide

We report measurement and analysis of the photodissociation spectrum of hydroxymethyl hydroperoxide (HOCH(2)OOH) and its partially deuterated analogue, HOCD(2)OOH, in the OH-stretching region. Spectra are obtained by Fourier transform infrared spectroscopy in the 1nu(OH) and 2nu(OH) regions, and by laser induced fluorescence detection of the OH fragment produced from dissociation of HOCH(2)OOH initiated by excitation of the 4nu(OH) and 5nu(OH) overtone regions (action spectroscopy). A one-dimensional local-mode model of each OH chromophore is used with ab initio calculated OH-stretching potential energy and dipole moment curves at the coupled-cluster level of theory. Major features in the observed absorption and photodissociation spectra are explained by our local-mode model. In the 4nu(OH) region, explanation of the photodissocation spectrum requires a nonuniform quantum yield, which is estimated by assuming statistical energy distribution in the excited state. Based on the estimated dissociation threshold, overtone photodissociation is not expected to significantly influence the atmospheric lifetime of hydroxymethyl hydroperoxide.     

Magnetization reversal in textured NdFeB-Fe composites observed by domain imaging

Textured composite samples consisting of Nd_13.6Fe_73.6Ga_0.6Co_6.6B_5.6 (MQU-F™) and micron-sized Fe particles with weight ratios from 100:0 to 70:30 have been prepared by hot deformation. Microstructure studies revealed a layered structure of both phases with the layer normal parallel to the pressing direction. Magnetic measurements showed single-phase hysteresis curves for all samples when measured along the pressing direction, which is also the easy axis of magnetization. Coercivity decreased drastically from 1.32 T for pure NdFeB samples to 0.154 T for a sample with 30 wt% Fe. Magneto-optical Kerr microscopy with a digitally enhanced imaging technique has been used to examine the evolution of magnetic domains in the hard and soft phase during demagnetizing a sample consisting of 70 wt% NdFeB and 30 wt% Fe. It is shown that demagnetization takes place via domain rearrangements within the soft phase, which lead to and support the nucleation of reversed interaction domains at phase boundaries. Also nucleation of interaction domains within the hard magnetic phase could be revealed.     

Skin‐worn Soft Microfluidic Potentiometric Detection System

A flexible skin‐mounted microfluidic potentiometric device for simultaneous electrochemical monitoring of sodium and potassium in sweat is presented. The wearable device allows efficient natural sweat pumping to the potentiometric detection chamber, containing solid‐contact ion‐selective Na⁺ and K⁺ electrodes, during exercise activity. The fabricated microchip electrolyte‐sensing device displays good analytical performance and addresses sweat mixing and carry‐over issues of early epidermal potentiometric sensors. Such soft skin‐worn microchip platform integrates potentiometric measurement, microfluidic technologies with flexible electronics for real‐time wireless data transmission to mobile devices. The new fully integrated microfluidic electrolyte‐detection device paves the way for practical fitness and health monitoring applications.     

Redox behavior and diffusion of copper in soda-lime-silica melts

Glasses with the base mol% composition xNa₂O · 10CaO · (90 ? x)SiO₂ with x = 10, 16, 20 and 26 were investigated at high temperatures using square-wave voltammetry. The recorded voltammograms exhibit two peaks. That at less negative or (depending on temperature and glass composition) even positive potential is attributed to the reduction of Cu²⁺ to Cu⁺, while that observed at more negative potential is caused by the reduction of Cu⁺ to metallic copper. For both redox steps, the peak potentials decrease linearly with temperature. Those of the composition with 10 mol% Na₂O show the most negative values. The diffusion coefficients can be fitted to Arrhenius equation. If referenced to the same viscosity, the diffusion coefficients decrease with increasing Na₂O-concentration. The effect of composition on the thermodynamics as well as on diffusivities is explained by the incorporation of the copper ions into the melt structure.