Do enzymes sleep and work?

Single-enzyme studies suggest that dynamic disorder is a general characteristic of enzyme catalysis.     

Flat map areal topography in Macaca mulatta based on combined MRI and histology

Flattened representations are a useful approach to represent the convoluted complex surface of the neocortex of primates and other large-brained mammals. In this study, we compared the flattened representation of neocortical areas obtained from the recently published MRI and histology atlas of the rhesus monkey brain (Saleem KS, Logothetis NK. A combined MRI and histology atlas of the rhesus monkey brain in stereotaxic coordinates. London: Academic; 2007) with other previously published maps. Our results confirm that flat map representations are advantageous due to their ease of use and that current flat maps are well comparable to each other. Some differences arise due to different distinguishing criteria and here too flat maps can help to reveal them.     

The D-optimal saturated designs of order 22

This paper attempts to prove the D-optimality of the saturated designs X${}^1$ and X${}^{11}$ of order 22, already existing in the current literature. The corresponding non-equivalent information matrices M${}^1$=(X${}^1$)${}^T$X${}^1$ and M${}^{11}$=(X${}^{11}$)${}^T$X${}^{11}$ have the maximum determinant. Within the application of a specific procedure, all symmetric and positive definite matrices M of order 22 with determinant the square of an integer and $\ge$det(M${}^1$) are constructed. This procedure has indicated that there are 26 such non-equivalent matrices M, for 24 of which the non-existence of designs X such that X${}^T$X =M is proved. The remaining two matrices M are the information matrices M${}^1$ and M${}^{11}$.     

The polynomial multidimensional Szemerédi Theorem along shifted primes

If $\vec q_1 ,...,\vec q_m $ : ? → ? ^? are polynomials with zero constant terms and E ? ? ^? has positive upper Banach density, then we show that the set E ∩ (E ? $\vec q_1 $ (p ? 1)) ∩ … ∩ (E ? $\vec q_m $ (p ? 1)) is nonempty for some prime p. We also prove mean convergence for the associated averages along the prime numbers, conditional to analogous convergence results along the full integers. This generalizes earlier results of the authors, of Wooley and Ziegler, and of Bergelson, Leibman and Ziegler.     

On‐Surface Reactive Planarization of Pt(II) Complexes

A series of Pt(II) complexes with tetradentate luminophores has been designed, synthesized, and deposited on coinage metal surfaces with the aim to produce highly planar self‐assembled monolayers. Low‐temperature scanning tunneling microscopy (STM) and density functional theory (DFT) calculations reveal a significant initial nonplanarity for all complexes. A subsequent metal‐catalyzed separation of the nonplanar moiety at the bridging unit via the scission of a C?N bond is observed, leaving behind a largely planar core complex. The activation barrier of this bond scission process is found to depend strongly on the chemical nature of both bridging group and coordination plane, and to increase from Cu(111) through Ag(111) to Au(111).     

Some physicochemical aspects of nanoparticulate magnetic iron oxide colloids in neat water and in the presence of poly(vinyl alcohol)

The preparation of magnetic iron oxide colloids directly from the coprecipitation of Fe (2+) and Fe (3+) species at different temperatures may lead to crystallites of higher size as the temperature of the reaction increases. On the other hand, dynamic light scattering investigations and dielectric measurements rather point to the similar colloidal size of the entities existing in their aqueous or solid-state dispersions, irrespective of the size of the primary nanocrystallites. Significant enhancement of the stability of the colloids, even in the presence of high electrolyte concentrations, is furnished after the addition of relatively small amounts of poly(vinyl alcohol), and the stabilization mechanism is discussed in terms of the various forces participating in the system. The experimental results suggest that the increased colloidal stability is triggered from the particles' decrease of velocity rather than from steric (entropic) effects originating from polymer absorption.     

Beta-cyclodextrin-appended giant amphiphile: aggregation to vesicle polymersomes and immobilisation of enzymes

A giant amphiphile consisting of polystyrene end-capped with permethylated beta-cyclodextrin was synthesised and found to form vesicular structures when injected as a solution in THF into water. The ability of the cyclodextrins on the surface of the polymersomes to form inclusion complexes with hydrophobic compounds was tested by carrying out a competition experiment with a fluorescent probe sensitive to the polarity of the surrounding medium. It was found that 1-adamantol can displace the fluorescent probe from the cavities of the cyclodextrin moieties of the polymersomes. The recognition of molecules by cell membranes in nature is often based on interactions with specific membrane receptors. To mimic this behaviour, the enzyme horseradish peroxidase was modified with adamantane groups through a poly(ethylene glycol) spacer and its interaction with the polymersomes was investigated. It was established that the presence of adamantane moieties on each enzyme allowed a host-guest interaction with the multifunctional surface of the polymersomes.     

The C-O stretch as an unprecedently large spectral marker for the electron transfer between Copper(II) and a phenolate anion

An unprecedented red shift of more than 200 cm(-1) in the vibrational frequency of the C-O bond in the [Cu(PhO)Ln]+ complex (PhO = phenoxy), dependent on the number n of additional ligands L, is reported. Upon change of n from 1 to 2, the spin density is shifted from the aromatic ring to the oxygen and copper atoms, which is reflected in the bond order and thus vibrational frequency of the C-O bond.     

Random differences in Szemerédi’s theorem and related results

We extend the interior gradient estimate due to Korevaar-Simon for solutions of the mean curvature equation from the case of euclidean graphs to the general case of Killing graphs. Our main application is the proof of existence of Killing graphs with prescribed mean curvature function for continuous boundary data, thus extending a result due to Dajczer, Hinojosa, and Lira. In addition, we prove the existence and uniqueness of radial graphs in hyperbolic space with prescribed mean curvature function and asymptotic boundary data at infinity.     

Water solubility, antioxidant activity and cytochrome C binding of four families of exohedral adducts of C60 and C70

Over the past decade, surface-modified, water soluble fullerenes have been shown by many different investigators to exhibit strong antioxidant activity against reactive oxygen species (ROS) in vitro and to protect cells and tissues from oxidative injury and cell death in vivo. Nevertheless, progress in developing fullerenes as bona fide drug candidates has been hampered by three development issues: 1) lack of methods for scalable synthesis; 2) inability to produce highly purified, single-species regioisomers compatible with pharmaceutical applications; and 3) inadequate understanding of structure-function relationships with respect to various surface modifications (e.g., anionic versus cationic versus charge-neutral polarity). To address these challenges, we have designed and synthesized more than a dozen novel water soluble fullerenes that can be purified as single isomers and which we believe can be manufactured to scale at reasonable cost. These compounds differ in addition pattern, lipophilicity and number and type of charge and were examined for their water solubility, antioxidant activity against superoxide anions and binding of cytochrome C. Our results indicate that dendritic water soluble fullerene[60] monoadducts exhibit the highest degree of antioxidant activity against superoxide anions in vitro as compared with trismalonate-derived anionic fullerenes as well as cationic fullerenes of similar overall structure. Among the higher adducts, anionic derivatives have a higher antioxidant activity than comparable cationic compounds. To achieve sufficient water solubility without the aid of a surfactant or co-solvent at least three charges on the addends are required. Significantly, anionic in contrast to cationic fullerene adducts bind with high affinity to cytochrome C.