Determination of sulfadiazine in phosphate- and DOC-rich agricultural drainage water using solid-phase extraction followed by liquid chromatography-tandem mass spectrometry

Trace levels of the veterinary antibiotic compound sulfadiazine (SDZ) can be determined in agricultural drainage water samples with this new method. Optimized sample pretreatment and solid-phase extraction was combined with liquid chromatography coupled to tandem mass spectrometry (SPE LC-MS/MS) using positive electrospray ionization. The linear dynamic range for the LC-MS/MS was assessed from 5 μg/L to 25 mg/L with a 15-point calibration curve displaying a coefficient of correlation r ²?=?0.9915. Agricultural drainage water spiked at a concentration of 25 ng/L gave recoveries between 63 and 98 % (relative standard deviation 15 %), while at 10 ng/L, it showed a lower recovery of 32 % (relative standard deviation 47 %). The final SPE LC-MS/MS method had a limit of detection (LOD)_Method and a limit of quantification (LOQ)_Method of 7.5 and 23 ng/L agricultural drainage water, respectively. Determination of SDZ, spiked at a realistic concentration of 50 μg/L, in artificial drainage water (ADW) containing common and high levels of phosphate (0.05, 0.5, and 5 mg/L) gave recoveries between 70 and 92 % (relative standard deviation 7.4–12.9 %). Analysis of the same realistic concentration of SDZ in ADW, spiked with common and high levels of dissolved organic carbon (2, 6, and 15 mg/L) confirmed the possible adaptation of a tandem solid-phase extraction (strong anion exchange (SAX)-hydrophilic-lipophilic balance (HLB)) followed by liquid chromatography-tandem mass spectrometry methodology. Recoveries obtained ranged from 104 to 109 % (relative standard deviation 2.8–5.2 %). The new methods enable determination of the veterinary antibiotic compound SDZ in agricultural drainage water from field experiments and monitoring schemes for phosphate- and dissolved organic carbon (DOC)-rich water samples in intensive farming areas.

Synthesis and characterization of ratiometric nanosensors for pH quantification: a mixed micelle approach

Optical nanoparticle pH sensors designed for ratiometric measurements have previously been synthesized using post-functionalization approaches to introduce sensor molecules and to modify nanoparticle surface chemistry. This strategy often results in low control of the nanoparticle surface chemistry and is prone to batch-to-batch variations, which is undesirable for succeeding sensor calibrations and cellular measurements. Here we provide a new synthetic approach for preparing nanoparticle pH sensors based on self-organization principles, which in comparison to earlier strategies offers a much higher design flexibility and high control of particle size, morphology and surface chemistry.     

Spin-dependent quasiparticle transport in aluminum single-electron transistors

We investigate the effect of Zeeman splitting on quasiparticle transport in normal-superconducting-normal (NSN) aluminum single-electron transistors (SETs). In the above-gap transport, the interplay of Coulomb blockade and Zeeman splitting leads to spin-dependence of the sequential tunneling. This creates regimes where either one or both spin species can tunnel onto or off the island. At lower biases, spin-dependence of the single quasiparticle state is studied, and operation of the device as a bipolar spin filter is suggested.     

Drug Delivery by an Enzyme‐Mediated Cyclization of a Lipid Prodrug with Unique Bilayer‐Formation Properties

Special delivery : Liposomal drug‐delivery systems in which prodrugs are activated specifically by disease‐associated enzymes have great potential for the treatment of severe diseases, such as cancer. A new type of phospholipid‐based prodrug has the ability to form stable small unilamellar vesicles (see picture). Activation of the prodrug vesicles by the enzyme sPLA₂ initiates a cyclization reaction, which leads to the release of the drug.

     

Alternative method for reconstruction of antihydrogen annihilation vertices

The ALPHA experiment, located at CERN, aims to compare the properties of antihydrogen atoms with those of hydrogen atoms. The neutral antihydrogen atoms are trapped using an octupole magnetic trap. The trap region is surrounded by a three layered silicon detector used to reconstruct the antiproton annihilation vertices. This paper describes a method we have devised that can be used for reconstructing annihilation vertices with a good resolution and is more efficient than the standard method currently used for the same purpose.     

Antihydrogen formation by autoresonant excitation of antiproton plasmas

In efforts to trap antihydrogen, a key problem is the vast disparity between the neutral trap energy scale ( $\sim\!50\,\upmu\mathrm{eV}$ ), and the energy scales associated with plasma confinement and space charge (~1 eV). In order to merge charged particle species for direct recombination, the larger energy scale must be overcome in a manner that minimizes the initial antihydrogen kinetic energy. This issue motivated the development of a novel injection technique utilizing the inherent nonlinear nature of particle oscillations in our traps. We demonstrated controllable excitation of the center-of-mass longitudinal motion of a thermal antiproton plasma using a swept-frequency autoresonant drive. When the plasma is cold, dense and highly collective in nature, we observe that the entire system behaves as a single-particle nonlinear oscillator, as predicted by a recent theory. In contrast, only a fraction of the antiprotons in a warm or tenuous plasma can be similarly excited. Antihydrogen was produced and trapped by using this technique to drive antiprotons into a positron plasma, thereby initiating atomic recombination. The nature of this injection overcomes some of the difficulties associated with matching the energies of the charged species used to produce antihydrogen.     

Automated Generation of Microkinetics for Heterogeneously Catalyzed Reactions Considering Correlated Uncertainties**

The study presents an ab-initio based framework for the automated construction of microkinetic mechanisms considering correlated uncertainties in all energetic parameters and estimation routines. 2000 unique microkinetic models were generated within the uncertainty space of the BEEF-vdW functional for the oxidation reactions of representative exhaust gas emissions from stoichiometric combustion engines over Pt(111) and compared to experiments through multiscale modeling. The ensemble of simulations stresses the importance of considering uncertainties. Within this set of first-principles-based models, it is possible to identify a microkinetic mechanism that agrees with experimental data. This mechanism can be traced back to a single exchange-correlation functional, and it suggests that Pt(111) could be the active site for the oxidation of light hydrocarbons. The study provides a universal framework for the automated construction of reaction mechanisms with correlated uncertainty quantification, enabling a DFT-constrained microkinetic model optimization for other heterogeneously catalyzed systems.