New access to lipo-chitooligosaccharide nodulation factors

Sulfonated and non-sulfonated lipo-chitooligosaccharides involved in Sinorhizobium meliloti-legume symbiosis are efficiently obtained on a multi mg scale by a 2-step procedure combining biotechnological and chemical approaches.     

Molecular tuning in highly fluorescent dithieno[3,2-b:2',3'-d]pyrrole-based oligomers: effects of N-functionalization and terminal aryl unit

A series of eight conjugated oligomers consisting of central dithieno[3,2-b:2',3'-d]pyrroles (DTPs) end-capped with either thienyl or phenyl groups have been prepared from N-alkyl-, N-aryl-, and N-acyl-dithieno[3,2-b:2',3'-d]pyrroles via Stille and Suzuki cross-coupling. The DTP-based quaterthiophene, N-phenyl-2,6-bis(2-thienyl)dithieno-[3,2-b:2',3'-d]pyrrole was characterized via X-ray crystallography and was found to crystallize in the orthorhombic space group Pna2(1) with a = 10.8666(3) ?, b = 22.8858(6) ?, c = 7.4246(2) ?, and Z = 4. The full oligomeric series was thoroughly investigated via photophysical, electrochemical, and DFT calculations in order to correlate the cumulative effects of both aryl end-groups and N-functionalization on the resulting optical and electronic properties. Through such molecular tuning, it was found to be possible to modulate the HOMO energy by as much as 0.32 V and to generate highly fluorescent oligomers with solution fluorescence efficiencies as high as 92%.     

β-Lactose in the View of a CFF-Optimized Force Field

Abstract

A recently developed force field PEF95SAC, based on Consistent Force Field (CFF) optimized potential energy parameters for alcohols and most of the naturally occurring carbohydrates, is applied to and tested on β-lactose. The properties of the potential energy surface of this disaccharide are compared to X-ray structures, NMR coupling constants and optical rotation data. The overall performance indicates good extrapolative power for the modeling of oligo- and polysaccharide structures. A new glycosidic linkage geometry region is proposed for β-lactose as being important in both solid state and water solutions. This finding is supported by calculated J _H,C coupling constants and calculated optical rotation values.

In relation to the spectral calculations on β-lactose, the error of the use of relative energies (ΔE) in place of the Gibbs free energy (ΔG) as the basis for calculating Boltzmann distributed properties is demonstrated. In the β-lactose case it is shown that the conformational entropy is neither negligible nor uniformly distributed over the potential energy surface.     

Enhanced monitoring of biopharmaceutical product purity using liquid chromatography-mass spectrometry

LC-MS is a widely used technique for impurity detection and identification. It is very informative and generates huge amounts of data. However, the relevant chemical information may not be directly accessible from the raw data map, particularly in reference to applications where unknown impurities are to be detected. This study demonstrates that multivariate statistical process control (MSPC) based on principal component analysis (PCA) in conjunction with multiple testing is very powerful for comprehensive monitoring and detection of an unknown and co-eluting impurity measured with liquid chromatography-mass spectrometry (LC-MS). It is demonstrated how a spiked impurity present at low concentrations (0.05% (w/w)) is detected and further how the contribution plot provides clear diagnostics of the unknown impurity. This tool makes a fully automatic monitoring of LC-MS data possible, where only relevant areas in the LC-MS data are highlighted for further interpretation.     

Interactions between Catalysts and Amphiphilic Structures and their Implications for a Protocell Model

One of the essential elements of any cell, including primitive ancestors, is a structural component that protects and confines the metabolism and genes while allowing access to essential nutrients. For the targeted protocell model, bilayers of decanoic acid, a single‐chain fatty acid amphiphile, are used as the container. These bilayers interact with a ruthenium–nucleobase complex, the metabolic complex, to convert amphiphile precursors into more amphiphiles. These interactions are dependent on non‐covalent bonding. The initial rate of conversion of an oily precursor molecule into fatty acid was examined as a function of these interactions. It is shown that the precursor molecule associates strongly with decanoic acid structures. This results in a high dependence of conversion rates on the interaction of the catalyst with the self‐assembled structures. The observed rate logically increases when a tight interaction between catalyst complex and container exists. A strong association between the metabolic complex and the container was achieved by bonding a sufficiently long hydrocarbon tail to the complex. Surprisingly, the rate enhancement was nearly as strong when the ruthenium and nucleobase elements of the complex were each given their own hydrocarbon tail and existed as separate molecules, as when the two elements were covalently bonded to each other and the resulting molecule was given a hydrocarbon tail. These results provide insights into the possibilities and constraints of such a reaction system in relation to building the ultimate protocell.     

Fruit tree model for uptake of organic compounds from soil

Apples and other fruits are frequently cultivated in gardens and are part of our daily diet. Uptake of pollutants into apples may therefore contribute to the human daily intake of toxic substances. In current risk assessment of polluted soils, regressions or models are in use, which were not intended to be used for tree fruits. A simple model for uptake of neutral organic contaminants into fruits is developed. It considers xylem and phloem transport to fruits through the stem. The mass balance is solved for the steady-state, and an example calculation is given. The Fruit Tree Model is compared to the empirical equation of Travis and Arms (T&A), and to results from fruits, collected in contaminated areas. For polar compounds, both T&A and the Fruit Tree Model predict bioconcentration factors fruit to soil (BCF, wet weight based) of > 1. No empirical data are available to support this prediction. For very lipophilic compounds (1ogK(ow) > 5), T&A overestimates the uptake. The conclusion from the Fruit Tree Model is that the transfer of lipophilic compounds into fruits is not relevant. This was also found by an empirical study with PCDD/F. According to the Fruit Tree Model, polar chemicals are transferred efficiently into fruits, but empirical data to verify these predictions are lacking.     

Large amplitude oscillatory elongation flow

A filament stretching rheometer (FSR) was used for measuring the elongation flow with a large amplitude oscillative elongation imposed upon the flow. The large amplitude oscillation imposed upon the elongational flow as a function of the time t was defined as where ε is the Hencky strain, is a constant elongational rate for the base elongational flow, Λ the strain amplitude (Λ ≥ 0), and Ω the strain frequency. A narrow molecular mass distribution linear polystyrene with a molecular weight of 145 kg/mol was subjected to the oscillative flow. The onset of the steady periodic regime is reached at the same Hencky strain as the onset of the steady elongational viscosity ( Λ = 0). The integral molecular stress function formulation within the ‘interchain pressure’ concept agrees qualitatively with the experiments.     

Measurement techniques in the testing of thin-walled structural members

The paper describes methods for measuring displacements and end moments in the testing of thin-walled columns. The complete spatial deformation of a column can be captured by using local and overall deformation measurement frames. The local frame involves spring-loaded levers and roller bearings to mount the frame on to the specimen. The overall frame slides along high-precision shafts using linear ball bearings. Fixed-ended bearings are used to measure minor and major axis bending moments as well as the applied load. The bearings allow the line of action of the applied force to be determined.