Improved fatty acid detection in micro-algae and aquatic meiofauna species using a direct thermal desorption interface combined with comprehensive gas chromatography-time-of-flight mass spectrometry

Comprehensive two-dimensional gas chromatography (GC x GC) with time-of-flight mass spectrometry detection is used to profile the fatty acid composition of whole/intact aquatic microorganisms such as the common fresh water green algae Scenedesmus acutus and the filamentous cyanobacterium Limnothrix sp. strain MRI without any sample preparation steps. It is shown that the technique can be useful in the identification of lipid markers in food-web as well as environmental studies. For instance, new mono- and diunsaturated fatty acids were found in the C(16) and C(18) regions of the green algae S. acutus and the filamentous cyanobacterium Limnothrix sp. strain MRI samples. These fatty acids have not, to our knowledge, been detected in the conventional one-dimensional (1D) GC analysis of these species due to either co-elution and/or their presence in low amounts in the sample matrix. In GC x GC, all congeners of the fatty acids in these microorganisms could be detected and identified due to the increased analyte detectability and ordered structures in the two-dimensional separation space. The combination of direct thermal desorption (DTD)-GC x GC-time-of-flight mass spectrometry (ToF-MS) promises to be an excellent tool for a more accurate profiling of biological samples and can therefore be very useful in lipid biomarker research as well as food-web and ecological studies.     

Determination of the carbon isotopic composition of whole/intact biological specimens using at-line direct thermal desorption to effect thermally assisted hydrolysis/methylation

In this paper, we discuss the use of a direct thermal desorption (DTD) interface as an alternative to Curie-point flash pyrolysis system as an inlet technique in gas chromatography-combustion isotope-ratio mass spectrometry (GC/C-IRMS) analysis of whole/intact phytoplankton and zooplankton specimens. The DTD in combination with a combipal auto-injector is programmed to perform the injection, evaporation of solvents, transport of capped programmed-temperature vaporizer (PTV) liners to the PTV injector and chemical derivatisation (thermally assisted hydrolysis/methylation; THM) such that a profile of a cellular fatty acids is obtained. Flow-cytometric sorted microalgae and handpicked zooplankton are used as samples with trimethylsulfonium hydroxide (TMSH) as methylating reagent. A major advantage of this novel approach over the Curie-point technique is the automation of the total procedure, which allows unattended analysis of large sample series. The profiles and delta(13)C carbon isotopic signatures of the fatty acid methyl esters (FAMEs) produced are very similar to those obtained using the Curie-point flash pyrolysis method. It is shown that algal samples must be kept no longer than 48 h in the DTD sample tray prior to the THM-analysis in order to maintain the integrity of their FAME profile.     

Formation of Highly Ordered Molecular Porous 2D Networks from Cyano-Functionalized Porphyrins on Cu(111)

We investigated the adsorption of three related cyano-functionalized tetraphenyl porphyrin derivatives on Cu(111) by scanning tunneling microscopy (STM) in ultra-high vacuum (UHV) with the goal to identify the role of the cyano group and the central Cu atom for the intermolecular and supramolecular arrangement. The porphyrin derivatives studied were Cu-TCNPP, Cu-cisDCNPP, and 2H-cisDCNPP, that is, Cu-5,10,15,20-tetrakis-(p-cyano)-phenylporphyrin, Cu-meso-cis-di(p-cyano)-phenylporphyrin and 2H-meso-cis-di(p-cyano)-phenylporphyrin, respectively. Starting from different structures obtained after deposition at room temperature, all three molecules form the same long-range ordered hexagonal honeycomb-type structure with triangular pores and three molecules per unit cell. For the metal-free 2H-cisDCNPP, this occurs only after self-metalation upon heating. The structure-forming elements are pores with a distance of 3.1 nm, formed by triangles of porphyrins fused together by cyano-Cu-cyano interactions with Cu adatoms. This finding leads us to suggest that two cyano-phenyl groups in the “cis” position is the minimum prerequisite to form a highly ordered 2D porous molecular pattern. The experimental findings are supported by detailed density functional theory calculations to analyze the driving forces that lead to the formation of the porous hexagonal honeycomb-type structure.     

What every chemist should know about plant names

Chemists screen plants for their constituents on a daily basis, and the data gathered is of importance to a wide range of fields such as medicine, evolutionary biology and ecology. However, the use of this data is sometimes impeded by incorrect citation of the species names. In this Viewpoint, I explain why chemists should be aware of the essentials of plant naming, and describe some easy quality checks that can be performed to avoid errors being perpetuated.     

Optimization of information content in a mass spectrometry based flow-chemistry system by investigating different ionization approaches

Current development in catalyst discovery includes combinatorial synthesis methods for the rapid generation of compound libraries combined with high-throughput performance-screening methods to determine the associated activities. Of these novel methodologies, mass spectrometry (MS) based flow chemistry methods are especially attractive due to the ability to combine sensitive detection of the formed reaction product with identification of introduced catalyst complexes. Recently, such a mass spectrometry based continuous-flow reaction detection system was utilized to screen silver-adducted ferrocenyl bidentate catalyst complexes for activity in a multicomponent synthesis of a substituted 2-imidazoline. Here, we determine the merits of different ionization approaches by studying the combination of sensitive detection of product formation in the continuous-flow system with the ability to simultaneous characterize the introduced [ferrocenyl bidentate+Ag]⁺ catalyst complexes. To this end, we study the ionization characteristics of electrospray ionization (ESI), atmospheric-pressure chemical ionization (APCI), no-discharge APCI, dual ESI/APCI, and dual APCI/no-discharge APCI. Finally, we investigated the application potential of the different ionization approaches by the investigation of ferrocenyl bidentate catalyst complex responses in different solvents.     

Generation of clean iron nanocrystals on an ultra-thin SiO(x) film on Si(001)

Upon exposure to Fe(CO)(5), the formation of pure cubic Fe nanocrystals with dimensions up to ~75 nm is reported on ultra-thin SiO(x) films (thickness ≈ 0.5 nm) on Si(001), which have been prepared in situ under UHV conditions. The active centers for initial decomposition of Fe(CO)(5) resulting in the growth of the Fe clusters are proposed to be SiO sites. After nucleation at these sites, further crystal growth is observed due to autocatalytic dissociation of Fe(CO)(5) at room temperature. The density of the Fe clusters can be increased by irradiating the surface with a focused electron beam (15 keV) prior to gas exposure. The formation of the active SiO sites upon electron irradiation is attributed to oxygen desorption via the Knotek-Feibelman mechanism.     

Defects in oxygen-depleted titanate nanostructures

The identification of defects and their controlled generation in titanate nanostructures is a key to their successful application in photoelectronic devices. We comprehensively explored the effect of vacuum annealing on morphology and composition of Na(2)Ti(3)O(7) nanowires and protonated H(2)Ti(3)O(7) nanoscrolls using a combination of scanning electron microscopy, Auger and Fourier-transform infrared (FT-IR) spectroscopy, as well as ab initio density functional theory (DFT) calculations. The observation that H(2)Ti(3)O(7) nanoscrolls are more susceptible to electronic reduction and annealing-induced n-type doping than Na(2)Ti(3)O(7) nanowires is attributed to the position of the conduction band minimum. It is close to the vacuum level and, thus, favors the Fermi level-induced compensation of donor states by cation vacancies. In agreement with theoretical predictions that suggest similar formation energies for oxygen and sodium vacancies, we experimentally observed the annealing induced depletion of sodium from the surface of the nanowires.     

A New Approach to Cycling in a 2-locus 2-allele Genetic Model

In the reproductive process new genetic types arise due to crossing over and recombination at the meiotic stage. A simplified biological model will be developed which incorporates this effect and the effect of selection. Although a chromosome may contain thousands of genes we will consider a simplified model consisting of two genetic loci, each containing two alleles of some gene.

The model will be then turned into a difference equation or mapping model x* = G(x,r) where x represents the frequency distribution of genotypes in a certain infinite population, x* is this distribution one generation later and r is the recombination parameter. For a certain choice of fitness and recombination parameters the mapping exhibits several fixed points. As r is varied one of the fixed points of the mapping loses its stability due to a conjugate pair of eigenvalues of the linearized mapping leaving the unit disk. It is shown that the required non-resonance conditions and “nonlinear damping” condition are satisfied and thus the fixed point undergoes a Neimark–Sacker bifurcation to a cycling or oscillatory state.

Once a cycling orbit is established one can conclude that genetic variation (over time) of the population can be maintained. This work reformulates and proves earlier observations of Alan Hastings in a way that makes the treatment of chromosomes with more genetic loci more straightforward.     

A conjecture on the stability of the periodic solutions of Ricker’s equation with periodic parameters

In this work, we propose a conjecture about the stability of the periodic solutions of the Ricker equation with periodic parameters, which goes beyond the existing theory, and for the special case of period-two parameters we analytically show the conjecture is true. For this case we show that the stability region in parameter space obtained from the conjecture is larger than a previously proposed stability region. The period-three case is investigated numerically and similar extensions are realized. This suggests that the current theory cited in this paper, while giving sufficient conditions for stability is far from optimal.     

Microscopic coexistence of superconductivity and magnetism in Ba(1-x)K(x)Fe2As2

It is widely believed that, in contrast to its electron-doped counterparts, the hole-doped compound Ba(1-x)K(x)Fe(2)As(2) exhibits a mesoscopic phase separation of magnetism and superconductivity in the underdoped region of the phase diagram. Here, we report a combined high-resolution x-ray powder diffraction and volume-sensitive muon spin rotation study of Ba(1-x)K(x)Fe(2)As(2) showing that this paradigm does not hold true in the underdoped region of the phase diagram (0≤x≤0.25). Instead we find a microscopic coexistence of the two forms of order. A competition of magnetism and superconductivity is evident from a significant reduction of the magnetic moment and a concomitant decrease of the magnetoelastically coupled orthorhombic lattice distortion below the superconducting phase transition.