Spin-peierls transition in dimerized stacks of anion-radical salt (N-Me-2,5-di-Me-Pz)(TCNQ)2, (Pz is pyrazine)

An anion-radical salt (ARS) (N-Me-2,5-di-Me-Pz)(TCNQ)₂, where Pz is pyrazine, was synthesized and its crystal structure was resolved. X-ray diffraction experiments on single crystals were performed. Heat capacity was measured in the temperature range from 2 to 300 K. Magnetisation and magnetic susceptibility were measured in the temperature range from 2 to 300 K and the low-temperature part was measured in magnetic fields from 5 mT to 5 T. The experimental results were explained in terms of dimerized Heisenberg spin chain model. Numerical calculations were performed and compared with experimental data.     

On the total mean curvature of a nonrigid surface

Using the Green’s theorem we reduce the variation of the total mean curvature of a smooth surface in the Euclidean 3-space to a line integral of a special vector field, which immediately yields the following well-known theorem: the total mean curvature of a closed smooth surface in the Euclidean 3-space is stationary under an infinitesimal flex.     

Diels-Alder ligation of peptides and proteins

The development of the Diels-Alder cycloaddition as a new method for the site-specific chemoselective ligation of peptides and proteins under mild conditions is reported. Peptides equipped with a 2,4-hexadienyl ester and an N-terminal maleimide react in aqueous media to give cycloadducts in high yields and depending on the amino acid sequence with high stereoselectivity. Except for the cysteine SH group the transformation is compatible with all amino acid side chain functional groups. For ligation to proteins the hexadienyl group was attached to avidin and streptavidin noncovalently by means of complex formation with a biotinylated peptide or by covalent attachment of a hexadienyl ester-containing label to lysine side chains incorporated into the proteins. Site-specific attachment of the hexadienyl unit into a Rab protein was achieved by means of expressed protein ligation followed by protection of the generated cysteine SH by means of Ellman's reagent. The protein reacted with different maleimido-modified peptides under mild conditions to give the fully functional cycloadducts in high yield. The results demonstrate that the Diels-Alder ligation offers an advantageous and technically straightforward new opportunity for the site-specific equipment of peptides and proteins with further functional groups and labels. It proceeds under very mild conditions and is compatible with most functional groups found in proteins. Its combination with other ligation methods, in particular expressed protein ligation is feasible.     

Plane contact problem for a prestressed incompressible elastic layer clamped along the base

The problem of a rigid punch penetration into the upper face of a layer is considered in the case of a homogeneous field of initial stresses. The model of isotropic incompressible nonlinearly elastic material determined by the Mooney potential is used. The case of rigid clamping of the layer along its lower face is considered under the assumption that the additional stresses caused by the penetrating punch are small compared with the initial ones. This assumption allows one to linearize the problem of determining the additional stresses. This problem is then reduced to solving an integral equations of the first kind with a difference kernel which allows one to determine the pressure in the contact region. An asymptotic solution is constructed for large values of the parameter characterizing the relative thickness of the layer. Amodified Multhopp-Kalandiyamethod is also used to obtain a solution for a wider range of the parameter.     

A numerical method for determining the strain rate intensity factor under plane strain conditions

Using the classical model of rigid perfectly plastic solids, the strain rate intensity factor has been previously introduced as the coefficient of the leading singular term in a series expansion of the equivalent strain rate in the vicinity of maximum friction surfaces. Since then, many strain rate intensity factors have been determined by means of analytical and semi-analytical solutions. However, no attempt has been made to develop a numerical method for calculating the strain rate intensity factor. This paper presents such a method for planar flow. The method is based on the theory of characteristics. First, the strain rate intensity factor is derived in characteristic coordinates. Then, a standard numerical slip-line technique is supplemented with a procedure to calculate the strain rate intensity factor. The distribution of the strain rate intensity factor along the friction surface in compression of a layer between two parallel plates is determined. A high accuracy of this numerical solution for the strain rate intensity factor is confirmed by comparison with an analytic solution. It is shown that the distribution of the strain rate intensity factor is in general discontinuous.     

The Low-Field Pulsed Mode Dynamic Nuclear Polarization in the Pentavalent Chromium Complex and Crude Oils

Measurements of the enhancement of the proton resonance signal right after applying the radiofrequency pulse with the variable duration in the magnetic field of about 100 Gauss on the homebuilt prototype of the dynamic nuclear polarization (DNP) spectrometer at near room temperature are presented. A dependence of the DNP enhancement of the solvent protons of the solution of the pentavalent chromium complex in ethylene glycol on the pumping pulse duration and incident pumping power is given. No DNP effect on the native protons of the crude oils and natural bitumen from the Russian oilfields is observed. A miserable DNP enhancement is registered on the protons of toluene by dissolving the crude oil and bitumen samples. The perspectives of using the results and technical solutions for geological exploration, studies of the asphaltene structures and their dynamics are discussed.     

Psoromic acid is a selective and covalent Rab-prenylation inhibitor targeting autoinhibited RabGGTase

Post-translational attachment of geranylgeranyl isoprenoids to Rab GTPases, the key organizers of intracellular vesicular transport, is essential for their function. Rab geranylgeranyl transferase (RabGGTase) is responsible for prenylation of Rab proteins. Recently, RabGGTase inhibitors have been proposed to be potential therapeutics for treatment of cancer and osteoporosis. However, the development of RabGGTase selective inhibitors is complicated by its structural and functional similarity to other protein prenyltransferases. Herein we report identification of the natural product psoromic acid (PA) that potently and selectively inhibits RabGGTase with an IC(50) of 1.3 μM. Structure-activity relationship analysis suggested a minimal structure involving the depsidone core with a 3-hydroxyl and 4-aldehyde motif for binding to RabGGTase. Analysis of the crystal structure of the RabGGTase:PA complex revealed that PA forms largely hydrophobic interactions with the isoprenoid binding site of RabGGTase and that it attaches covalently to the N-terminus of the α subunit. We found that in contrast to other protein prenyltransferases, RabGGTase is autoinhibited through N-terminal (α)His2 coordination with the catalytic zinc ion. Mutation of (α)His dramatically enhances the reaction rate, indicating that the activity of RabGGTase is likely regulated in vivo. The covalent binding of PA to the N-terminus of the RabGGTase α subunit seems to potentiate its interaction with the active site and explains the selectivity of PA for RabGGTase. Therefore, psoromic acid provides a new starting point for the development of selective RabGGTase inhibitors.     

Comments on article “symmetric heat and mass transfer in a rotating spherical layer,” <Emphasis Type="Italic">JETP</Emphasis> 94 (3), 459 (2002)

Analytic solutions to the heat and mass transfer equations, which were obtained in [1], are corrected. It is shown that the dependence of the growth rate of the Earth’s inner core on heat flux changes in this case.     

Interfacial layers from the protein HFBII hydrophobin: dynamic surface tension, dilatational elasticity and relaxation times

The pendant-drop method (with drop-shape analysis) and Langmuir trough are applied to investigate the characteristic relaxation times and elasticity of interfacial layers from the protein HFBII hydrophobin. Such layers undergo a transition from fluid to elastic solid films. The transition is detected as an increase in the error of the fit of the pendant-drop profile by means of the Laplace equation of capillarity. The relaxation of surface tension after interfacial expansion follows an exponential-decay law, which indicates adsorption kinetics under barrier control. The experimental data for the relaxation time suggest that the adsorption rate is determined by the balance of two opposing factors: (i) the barrier to detachment of protein molecules from bulk aggregates and (ii) the attraction of the detached molecules by the adsorption layer due to the hydrophobic surface force. The hydrophobic attraction can explain why a greater surface coverage leads to a faster adsorption. The relaxation of surface tension after interfacial compression follows a different, square-root law. Such behavior can be attributed to surface diffusion of adsorbed protein molecules that are condensing at the periphery of interfacial protein aggregates. The surface dilatational elasticity, E, is determined in experiments on quick expansion or compression of the interfacial protein layers. At lower surface pressures (<11 mN/m) the experiments on expansion, compression and oscillations give close values of E that are increasing with the rise of surface pressure. At higher surface pressures, E exhibits the opposite tendency and the data are scattered. The latter behavior can be explained with a two-dimensional condensation of adsorbed protein molecules at the higher surface pressures. The results could be important for the understanding and control of dynamic processes in foams and emulsions stabilized by hydrophobins, as well as for the modification of solid surfaces by adsorption of such proteins.