Relationship between conformational flexibility and chelate cooperativity

A family of four biscarbamates (AA) and four bisphenols (DD) were synthesized, and H-bonding interactions between all AA?DD combinations were characterized using (1)H NMR titrations in carbon tetrachloride. A chemical double mutant cycle analysis shows that there are no secondary electrostatic interactions or allosteric cooperativity in these systems, and the system therefore provides an ideal platform for investigating the relationship between chemical structure and chelate cooperativity. Effective molarities (EMs) were measured for 12 different systems, where the number of rotors in the chains connecting the two H-bond sites was varied from 5 to 20. The association constants vary by less than an order of magnitude for all 12 complexes, and the variation in EM is remarkably small (0.1-0.9 M). The results provide a relationship between EM and the number of rotors in the connecting chains (r): EM ≈ 10r(-3/2). The value of 10 M is the upper limit for the value of EM for a noncovalent intramolecular interaction. Introduction of rotors reduces the value of EM from this maximum in accord with a random walk analysis of the encounter probability of the chain ends (r(-3/2)). Noncovalent EMs never reach the very high values observed for covalent processes, which places limitations on the magnitudes of the effects that one is likely to achieve through the use of chelate cooperativity in supramolecular assembly and catalysis. On the other hand, the decrease in EM due to the introduction of conformational flexibility is less dramatic than one might expect based on the behavior of covalent systems, which limits the losses in binding affinity caused by poor preorganization of the interaction sites.     

Cooperativity, partially bound states, and enthalpy-entropy compensation

Efforts to develop a quantitative understanding of molecular recognition rely on the additivity of individual intermolecular interactions, and cooperativity represents one of the major potential stumbling blocks. A chemical double-mutant cycle has been used to experimentally measure cooperativity between functional group interactions within a complex framework. The interaction between two aromatic groups varies by 0.2 +/- 0.4 kJ mol(-1) in synthetic H-bonded complexes that differ by 8-13 kJ mol(-1) in overall stability. In these systems, the free energies associated with individual intermolecular interactions can therefore be reliably treated in an additive fashion. The results suggest that alternative explanations should be considered for cooperative phenomena observed in other systems, and a rationale based on the population of partially bound states in flexible molecules is proposed to account for the enthalpic chelate effect and enthalpy-entropy compensation.     

Evolution of near‐surface deformed layers during hot rolling of AA3104 aluminium alloy

In the present study, controlled reheating and breakdown rolling experiments have been carried out and the thickness, structure and uniformity of the resultant near‐surface deformed layer have been characterised by scanning and transmission electron microscopy. High aspect ratio rolling, coupled with an increased rolling speed and rough and worn roll surfaces results in a high degree of interaction between the work roll and work pieces. This generates a shingled surface appearance with a high population of transverse surface cracks and a relatively thick near‐surface deformed layer. In contrast, relatively low aspect ratio rolling, coupled with a reduced rolling speed and freshly ground work roll surfaces generates a relatively thin near‐surface deformed layer. The thickness of the near‐surface deformed layer varies across the alloy surface and is directly related to the shingles, the surface cracks and the distribution of coarse intermetallics. Copyright © 2009 John Wiley & Sons, Ltd.     

Individuality Normalization when Labeling with Isotopic Glycan Hydrazide Tags (INLIGHT): A Novel Glycan-Relative Quantification Strategy

The Individuality Normalization when Labeling with Isotopic Glycan Hydrazide Tags (INLIGHT) strategy for the sample preparation, data analysis, and relative quantification of N-linked glycans is presented. Glycans are derivatized with either natural (L) or stable-isotope labeled (H) hydrazide reagents and analyzed using reversed phase liquid chromatography coupled online to a Q Exactive mass spectrometer. A simple glycan ladder, maltodextrin, is first used to demonstrate the relative quantification strategy in samples with negligible analytical and biological variability. It is shown that after a molecular weight correction attributable to isotopic overlap and a post-acquisition normalization of the data to account for any systematic bias, a plot of the experimental H:L ratio versus the calculated H:L ratio exhibits a correlation of unity for maltodextrin samples mixed in different ratios. We also demonstrate that the INLIGHT approach can quantify species over four orders of magnitude in ion abundance. The INLIGHT strategy is further demonstrated in pooled human plasma, where it is shown that the post-acquisition normalization is more effective than using a single spiked-in internal standard. Finally, changes in glycosylation are able to be detected in complex biological matrices, when spiked with a glycoprotein. The ability to spike in a glycoprotein and detect change at the glycan level validates both the sample preparation and data analysis strategy, making INLIGHT an invaluable relative quantification strategy for the field of glycomics.

Acetals: a new organocatalysis chemotype for one-pot enantioselective α-amination

Conditions are described for one-pot Brønsted acid and organocatalysed enantioselective α-amination of acetals and associated functionalities. Of the organocatalysts screened, proline tetrazole gave the highest ee, while aqueous monochloroacetic acid proved to be the best Brønsted acid activator regarding minimizing racemization and maximizing product yield. The reaction opens up the way for using masked carbonyl functionalities in organocatalysis.     

A rapid heating and high magnetic field thermal analysis technique

Journal of Thermal Analysis and Calorimetry - A new thermal analysis technique is described that allows measurements to be performed on bulk samples at extreme heating and cooling rates and in high...     

Chemistry-Performance Relationships of Polymer Gel-Electrolytes for Mg−S and Li−S Batteries: Influence of Network Cation Solvation Capacity on Polymer-Polysulfide Interactions

Metal-sulfur batteries are a promising next-generation energy storage technology, offering high theoretical energy densities with low cost and good sustainability. An active area of research is the development of electrolytes that address unwanted migration of sulfur and intermediate species known as polysulfides during operation of metal-sulfur batteries, a phenomenon that leads to low energy efficiency and short life-spans. A particular class of electrolytes, gel polymer electrolytes, are especially attractive for their ability to repel polysulfides on the basis of structure, electrostatics, and other polymer properties. Herein, within the context of magnesium- and lithium-sulfur batteries, we investigate the impact of gel polymer electrolyte cation solvation capacity, a property related to network dielectric constant and chemistry, on sulfur/polysulfide-polymer interactions, an understudied property-performance relationship. Polymers with lower cation solvation capacity are found to permanently absorb less polysulfide active material, which increases sulfur utilization for Li−S batteries and significantly increases charge efficiency and life-span for Li−S and Mg−S batteries.     

Diagnostic cellular organization features extracted from autofluorescence images

Depth-resolved NADH autofluorescence images are shown to differentiate between normal and precancerous engineered tissues. An inverse power law behavior of the power spectral density (PSD) of these images is observed, indicating a self-affine organization of mitochondrial NADH at length scales 1-10 microm. Power exponents of the PSD functions vary significantly with tissue depth and precancerous state, giving insight into the morphological changes associated with precancerous lesions and providing substantial potential for noninvasive clinical diagnosis of squamous epithelial lesions and tumors.