Generation and dissociation pathways of singly and doubly protonated bisguanidines in the gas phase

Para-bisguanidinyl benzene 1 and its N-permethylated derivative 2 are both sufficiently strong bases to afford not only the monocations [1+H]+ and [2+H]+, but also the doubly protonated ions, [1+2H]2+ and [2+2H]2+, in the gas phase. The title ions generated via electrospray ionization are probed by collision-induced dissociation experiments which inter alia reveal that the dicationic species [1+2H]2+ and [2+2H]2+ can even undergo fragmentation reactions with maintenance of the 2-fold charge. Complementary results from density functional theory predict PAs above 1000 kJ mol(-1) for the neutral compounds, i.e., PA(1) = 1025 kJ mol(-1) and PA(2) = 1067 kJ mol(-1). Due to the stabilization of the positive charge in the guanidinium ions and the para-phenylene spacer separating the basic sites, even the monocations bear sizable proton affinities, i.e., PA([1+H]+) = 740 kJ mol(-1) and PA([2+H]+) = 816 kJ mol(-1).     

Surface structural investigation of starch-based biomaterials

Surface structural characterisation of three different starch-based blends (with poly[ethylene-co-(vinyl alcohol)], cellulose acetate and polycaprolactone) was carried out. The results show that there is a difference between the bulk and the surface composition of all studied blends. Two different hypotheses were investigated - predominant presence of a synthetic component on the surface and possible inter- and/or intramolecular bonds. The results were related to previous data for cell behaviour on those materials. It was found that both surface hydrophilicity and surface functionality are of great importance for cell adhesion and growth on starch-based biomaterials.     

Molecular weight and configurational stability of poly[(fluorophenyl)acetylene]s prepared with metathesis and insertion catalysts

Series of high‐cis and cis/trans poly[(fluorophenyl)acetylene]s (PFPhA) have been prepared by polymerization of (2‐fluorophenyl)acetylene, (3‐fluorophenyl)acetylene, and (4‐fluorophenyl)acetylene with catalysts: [Rh(1,5‐cyclooctadiene) OCH₃]₂ (high‐cis PFPhAs) and tungsten(VI) oxychloride/tetraphenyltin (cis/trans PFPhAs). The molecular weight and configurational stability under various conditions at room temperature were studied for both PFPhAs series by means of size exclusion chromatography, ¹H‐NMR, and UV‐vis techniques. All samples exhibited slow degradation when exposed to the atmosphere in the solid state; the rate of degradation was independent on the F‐position on the Ph ring. The rate of degradation increased up to three orders of magnitude in the tetrahydrofuran solution where it was higher for high‐cis polymers compared with their cis/trans counterparts. The degradation of high‐cis PFPhAs was accompanied by significant cis‐to‐trans isomerization in aerated tetrahydrofuran solution. Rate of degradation and isomerization exhibited the same dependence on the F‐position on the Ph ring. The hypothesis was postulated that the degradation of high‐cis PFPhAs in solution was accelerated by cis‐to‐trans isomerization due to which the content of unpaired electrons on the main chains is enhanced. In both high‐cis and cis/trans series of polymers the ortho‐substituted isomers exhibited an enhanced stability compared with meta‐ and para‐substituted isomers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4296–4309, 2010     

Schur-convexity and the Simpson formula

The main objective of this work is to give a necessary and sufficient condition for the function defined as the difference of the Simpson quadrature rule and the arithmetic integral mean to be Schur-convex.     

Preparation of Ethyl Esters of Protected 3-Aryl-2,3-Diaminopropanoic Acids by Reaction of Ethyl N-(Diphenylmethylene)glycinate and Azomethines1

Ethyl 3-aryl-3-arylamino-2-[(diphenylmethylene)amino]propanoates 3 are prepared by phase-transfer catalyzed reaction of ethyl N-(diphenylmethylene)-glycinate and azomethines.     

Simple methods for characterization of metals in historical textile threads

Characterization of metal threads on historical textile materials is important for preservation of valuable cultural heritage. Obtained results dictate decisions on cleaning, conservation and restoration steps. The most important part of characterization is chemical analysis of originally applied materials, since this enables understanding the nature of chemical and physical degradation and determines the cleaning methods. Methods applied should be non-destructive and sensitive enough to detect trace elements in small sample amounts. The goal of this research was to describe the most useful procedures for fast and simple determination of specific metals of interest. Therefore we propose application of scanning electron microscopy equipped with EDS detector (SEM-EDS) for sample surface analysis and inductively coupled plasma-optical emission spectroscopy (ICP-OES) for chemical analysis of metals threads. For quality insurance reasons, a comparative method applied for chemical analysis was atomic absorption spectrometry (AAS). This combination of methods has proven to be very useful in analysis of historical samples, since SEM-EDS was a simple and non-destructive method which provided information on chemical composition of sample surfaces, while ICP-OES and AAS enabled the full insight into the average chemical composition of samples. Nevertheless, both ICP-OES and AAS were destructive methods which demanded dissolving of samples prior to the analysis. In this work nine different metal fibers collected from historical textile materials were characterized. Proposed methods enabled obtaining information on sample constitution, morphology, topology and chemical composition.     

Fungal glycoside hydrolases for saccharification of lignocellulose: outlook for new discoveries fueled by genomics and functional studies

Genome sequencing of a variety of fungi is a major initiative currently supported by the Department of Energy’s Joint Genome Institute. Encoded within the genomes of many fungi are upwards of 200+ enzymes called glycoside hydrolases (GHs). GHs are known for their ability to hydrolyze the polysaccharide components of lignocellulosic biomass. Production of ethanol and “next generation” biofuels from lignocellulosic biomass represents a sustainable route to biofuels production. However, this process has to become more economical before large scale operations are put into place. Identifying and characterizing GHs with improved properties for biomass degradation is a key factor for the development of cost effective processes to convert biomass to fuels and chemicals. With the recent explosion in the number of GH encoding genes discovered by fungal genome sequencing projects, it has become apparent that improvements in GH gene annotation processes have to be developed. This will enable more informed and efficient decision making with regard to selection and utilization of these important enzymes in bioprocess that produce fuels and chemicals from lignocellulosic feedstocks.     

Numerical Studies of Viscoelastic Flow Using the Software OpenFOAM

Viscoelastic fluids are a special class of non-Newtonian fluids. There are several types of viscoelastic fluid models, and all of them have a complex rheological response in comparison to Newtonian fluids. This response can be viewed as a combination of viscous and elastic effects and non-linear phenomena. This complex physics makes a numerical simulation a rather challenging task, even in simple test-cases. Studies presented in this paper are numerical studies of the viscoelastic fluid flow in several test cases. These studies have been done in OpenFOAM, an open-source CFD package. Implementation of viscoelastic models and a solver is only available in a community driven version of software (OpenFOAM-ext). One of the goals of research in this paper was to test the solver and models on some simple test cases. We considered start-up and pulsating flows of viscoelastic fluid in a channel and a circular pipe. The important thing is that an analytical solution can be found in these cases, making in possible to test all aspects of numerical simulation in OpenFOAM. Obtained results showed an excellent agreement with the analytical solution for both velocity and stress components. These results encouraged authors' motivation and a choice to use OpenFOAM for simulation of viscoelastic flows. We hope that our research will make a contribution to the OpenFOAM community. Our plan for the further research is a simulation of blood flow in arteries with the viscoelastic solver. (© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)