Automated and rapid online determination of 15N abundance and concentration of ammonium, nitrite, or nitrate in aqueous samples by the SPINMAS technique

On the basis of the principle of reaction continuous-flow quadrupole mass spectrometry, an automated sample preparation unit for inorganic nitrogen (SPIN) species was developed and coupled to a quadrupole Mass Spectrometer (MAS). The SPINMAS technique was designed for an automated, sensitive, and rapid determination of 15N abundance and concentration of a wide variety of N-species involved in nitrogen cycling (e.g. NH4+, NO3-, NH2OH etc.). In this paper, the SPINMAS technique is evaluated with regard to the determination of 15N abundance and concentration of the most fundamental inorganic nitrogen compounds in ecosystems such as NH4+, NO2-, and NO3-. The presented paper describes the newly developed system in detail and demonstrates the general applicability of the system. For a precise determination of 15N abundance and concentration, a minimum total N-amount of 10 microg NH4+ - N, 0.03 microg NO2- - N, or 0.3 microg NO3- - N has to be supplied. Currently, the SPINMAS technique represents the most rapid and only fully automated all-round method for a simultaneous determination of 15N abundance and total N-amount of NH4+, NO2-, or NO3- in aqueous samples.     

Local near field assisted ablation of fused silica

In this contribution we present recent experimental and theoretical results on local near-field assisted laser ablation. Along these lines, we have generated sub-diffraction sized nanostructures on fused silica substrates, exploiting the local near fields of highly ordered triangular gold nanoparticle arrays generated by nanosphere lithography. After preparation, the nanoparticle arrays were irradiated with a single 35 fs long laser pulse with a central wavelength of λ=790 nm. The pulse energy was set to E=3.9 μJ, resulting in a fluence well below the ablation threshold of the fused silica substrates. In addition, 3D electromagnetic simulations using a finite integration technique in time domain have been performed. The simulations demonstrate that indeed the local field in the vicinity of the tips of the triangular nanoparticles overcome the ablation threshold and easily explain the generated nanostructures. Most importantly, the simulations show, that higher order modes contribute to the ablation process. These modes cause ablation along the side edges of the nanoparticles. Finally, we demonstrate, that the optical properties of the triangular nanoparticles, which can be tuned by their morphology, are crucial parameters for the generation of the ablation structures.     

Antiviral activity of Engystol<Superscript>®</Superscript> and Gripp-Heel<Superscript>®</Superscript>: an in-vitro assessment

Background  

Infections with respiratory viruses can activate the innate immune response - an important host defence mechanism in the early stage of viral infection. Interferon (IFN) release, triggered by virus infection, is an important factor in establishing an antiviral state, where IFN activation occurs prior to the onset of the adaptive immune response.     

Polyelectrolyte–protein interaction at low ionic strength: required chain flexibility depending on protein average charge

The effect of low ionic strength leading to reduced polyelectrolyte–protein interactions has been shown by in silico and in vitro experiments, suggesting polyelectrolyte rigidity increasing at low ionic strength, thus leading to reduced interactions with proteins. This contribution elucidates polyelectrolyte–protein precipitation in the 0–2.6-mS?cm^?1 ionic strength regime with polyelectrolyte rigidity determinations, using viscosimetry at these conditions, also considering protein charge distributions, using different proteins. Precipitation yields increased from 5 to 40 % at low ionic strength to up to 90 % at intermediate ionic strength, depending on protein and polyelectrolyte type, using lysozyme and three different monoclonal antibodies. Comparing precipitation behavior of the monoclonal antibodies, a qualitative correlation between required polyelectrolyte flexibility to enhance protein precipitation and protein average charge as well as hydrophobicity of the antibodies was discovered. Antibodies with lower average charge and less hydrophobicity required more flexible polyelectrolytes to enhance precipitation behavior by allowing interaction of the polyelectrolytes with proteins, attaching to positively charged protein patches while “circumnavigating” negatively charged protein areas. In contrast, antibodies with higher protein average charge showed increasing precipitation yields up to 90 % already at lower ionic strength, associated with then more rigid polyelectrolyte structures. Therefore, designing polyelectrolytes with specific chain flexibility could help to improve precipitation behavior toward specific target proteins in polyelectrolyte-driven purification techniques.     

Editorial

JPC – Journal of Planar Chromatography – Modern TLC -     

Growth of one-dimensional Pd nanowires on the terraces of a reduced SnO2(101) surface

Palladium, vapor-deposited at room temperature on a reduced SnO2(101) surface, forms one-dimensional islands, one atomic layer high, 5 A wide, and up to 350 A long. Scanning tunneling microscopy shows that neighboring islands do not merge. First-principles calculations reveal the atomistic processes that lead to this, for metal oxide substrates unusual, overlayer growth. Formation of 1D islands is mediated by a large anisotropy in surface diffusion, strong Pd-Sn interaction, and the lack of stable binding sites at the sides of the Pd islands. Nucleation is defect mediated, and the initial nucleation site determines the width of the resulting nanocluster.     

Two-loop virtual top-quark effect on Higgs-boson decay to bottom quarks

In most of the mass range encompassed by the limits from the direct search and the electroweak precision tests, the Higgs boson of the standard model preferably decays to bottom quarks. We present, in analytic form, the dominant two-loop electroweak correction, of O(GF2mt4), to the partial width of this decay. It amplifies the familiar enhancement due to the O(GFmt2) one-loop correction by about +16% and thus more than compensates the screening by about -8% through strong-interaction effects of order O(alphasGFmt2).     

Cyanines comprising barbiturate group facilitate NIR-light assisted ATRP under anaerobic and aerobic conditions at two wavelengths using Fe(III) catalyst

Cyanines with heptamethine pattern namely 5-(6-(2-(3-ethyl-1,1-dimethyl-1H-benzo[e]indol-2(3H)-ylidene)ethylidene)-2-(2-(3-ethyl-1,1-dimethyl-1H-benzo[e]indol-3-ium-2yl) vinyl) cyclo-hex-1-en-1-yl)-1,3-dimethyl-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-4-olate comprising a barbiturate group facilitate controlled radical polymerization using FeBr₃ in the ppm range applying radiation at 790 nm. Tris(4-methoylphenyl)phosphine, Tris(2-pyridylmethyl)amine or tetrabutylammonium bromide served as ligand. The latter showed the best performance resulting in a system needing no amino nitrogen for photo-ATRP. Ethyl α-bromophenylacetate worked as initiator. The cyanine interacts with FeBr₃ resulting in a new absorption band at 877 nm that also resulted in formation of polymer exhibiting similar molecular weight but higher dispersity compared to that obtained by 790 nm radiation by exposure with a light-emitting diode (LED) emitting at 870 nm. This explains the reactivity of the system while other cyanines such as 2-[2-[3-[2-(1,3-Dihydro-1,3,3-trimethyl-2H-indol-2-ylidene)-ethylidene]-2-(1-phenyl- 1H-tetrazol-5-ylsulfanyl)-1-cyclohexen-1-yl]-ethenyl]-1,3,3-trimethyl-3H-indolium chloride showed no activity by exposure at 790 nm in combination with FeBr₃/Br⁻. Controlled radical polymerization was confirmed by successful chain extension and block copolymerization experiments resulting in polymers, which exhibit a dispersity of about 1.3. Interestingly, the new system comprising the aforementioned barbiturate substituted cyanine, FeBr₃/Br⁻ and ethyl α-bromophenylacetate showed a certain oxygen tolerance. Polymers obtained exhibited similar dispersity as those made under inert conditions.     

Physical boundaries within aggregates – differences between amorphous,para‐crystalline,and crystalline Structures

The structural properties of finely divided inorganic materials such as metal and metalloid oxides, silicates or carbonates of both synthetic and natural origin are compared by means of electron microscopy and tomography. The structure of the outer surfaces of various compact or compacted agglomerates may suggest some striking similarities between various amorphous silica on the one hand and crystalline titania and alumina on the other however the details of the interior fine structure are completely different. Inside of the crystalline aggregates of, for example, alumina and titania distinct grain boundaries between the inter‐grown primary crystallites exist. Also physical boundaries between different solid phases and crystalline/amorphous transitions in core/shell structures can occur. No physical grain or phase boundaries were found inside of synthetic amorphous silica or para‐crystalline carbon black thus, the aggregate is the constituent particle. Synthetic amorphous silica from different production technologies (fumed/pyrogenic, precipitated, aerogel, gel) may exhibit different macro‐morphology but distinct similarities of the amorphous silica networks. Computational studies on silica and titania underline the stability of constituent particles and aggregates as observed by means of TEM after dispersing the original materials by ultra‐sonication.