Chemistry of Lipid A: At the Heart of Innate Immunity

In many Gram‐negative bacteria, lipopolysaccharide (LPS) and its lipid A moiety are pivotal for bacterial survival. Depending on its structure, lipid A carries the toxic properties of the LPS and acts as a potent elicitor of the host innate immune system via the Toll‐like receptor 4/myeloid differentiation factor 2 (TLR4/MD‐2) receptor complex. It often causes a wide variety of biological effects ranging from a remarkable enhancement of the resistance to the infection to an uncontrolled and massive immune response resulting in sepsis and septic shock. Since the bioactivity of lipid A is strongly influenced by its primary structure, a broad range of chemical syntheses of lipid A derivatives have made an enormous contribution to the characterization of lipid A bioactivity, providing novel pharmacological targets for the development of new biomedical therapies. Here, we describe and discuss the chemical aspects regarding lipid A and its role in innate immunity, from the (bio)synthesis, isolation and characterization to the molecular recognition at the atomic level.     

Quasi-SMILES: quantitative structure–activity relationships to predict anticancer activity

Molecular Diversity - Reliable prediction of anticancer potential of different substances for different cells using unambiguous algorithms is attractive alternative of experimental investigation of...     

Periodic subgroups of projective linear groups in positive characteristic

We classify the maximal irreducible periodic subgroups of PGL(q, ), where is a field of positive characteristic p transcendental over its prime subfield, q = p is prime, and ^× has an element of order q. That is, we construct a list of irreducible subgroups G of GL(q, ) containing the centre ^×1 _q of GL(q, ), such that G/ ^×1 _q is a maximal periodic subgroup of PGL(q, ), and if H is another group of this kind then H is GL(q, )-conjugate to a group in the list. We give criteria for determining when two listed groups are conjugate, and show that a maximal irreducible periodic subgroup of PGL(q, ) is self-normalising.      

Influence of arm length and number on star-shaped poly(2-isopropyl-2-oxazoline) aggregation in aqueous solutions near cloud point

Four-arm star-shaped poly(2-isopropyl-2-oxazolines) (PiPrOx₄) are synthesized by cationic polymerization on t-butylcalix[4]arene macroinitiator. The obtained samples differ by polymerization degree of arms N_PiPrOx = 9 and 25 and are characterized in chloroform. The behavior in aqueous solutions is studied by light scattering methods and compared with the results of investigation of eight-arm star with similar structure. Three types of particles are observed in solution of short-arm PiPrOx₄ at room temperature, whereas only two particle types are present in long-arm star solution. Arm shortening leads to widening of the phase transition interval. The arm number decreasing reduces the phase transition temperature by 1°C.     

Formation of mesoscopic water networks in aqueous systems

Formation of the macroscopically-infinite hydrogen-bonded water network in various aqueous systems occurs via 3D percolation transition when the probability of finding a spanning water cluster exceeds 95%. As a result, in a wide interval of water content below the percolation threshold, rarefied quasi-2D water networks span over the mesoscopic length scale. Formation and topology of spanning water networks, which affect various properties of aqueous systems, can be described within the framework of the percolation theory.     

A practical one-pot synthesis of vinylstannanes from ketones

Treatment of ketones with Bu3SnLi followed by addition of MsCl/Et3N to the resulting alkoxide provides vinylstannanes. Cyclic vinylstannanes are particularly amenable to this procedure and isolated yields of 81-83% could be consistently attained. Traces of Bu3SnH in crude reaction products could be removed by stirring in CHCl3 with a catalytic amount of AIBN followed by filtration through silica gel.     

Simple and fast method for the fabrication of switchable bicomponent micropatterned polymer surfaces

We report on the fabrication of micropatterned polymer surfaces that allow the reversible inversion of surface topography, charge, and wettability. Micropatterned surfaces were prepared by grafting two oppositely charged polyelectrolytes (poly(acrylic acid) and poly(2-vinylpyridine)) using a combination of photolithography, "lift off", and "grafting to" techniques. The switchable surfaces are of interest in microprinting and for the design of microfluidic devices and programmed protein adsorption.     

Conductivity, magnetoresistance, and the Hall effect in granular Fe/SiO2 films

We have investigated the conductance, magnetoresistance, and Hall effect in granular Fe/SiO₂ films with size of the iron grains around 40 Å, whose volume fraction x lies in the range 0.3–0.7. The conduction activation regime has been established for x<0.6. On the insulator side of the transition we observed a giant negative magnetoresistance, falling off sharply as the metal volume fraction decreases. For x<0.4 we observed a large positive magnetoresistance of premagnetized samples, showing up in fields; ～100 Oe and characterized by large response times. The field dependence of the Hall effect in the dielectric samples, as in the metallic samples, correlates with their magnetization. We found that the Hall resistance is proportional to the square root of the longitudinal resistance, which cannot be explained by known models of the anomalous Hall effect.