Thermodynamics of interactions of water-soluble porphyrins with RNA duplexes

We characterized the interactions of meso-tetrakis(4N-(2-hydroxyethyl)pyridinium-4-yl) porphyrin (TEtOHPyP4), meso-tetrakis(4N-allylpyridinium-4-yl) porphyrin (TAlPyP4), and meso-tetrakis(4N-metallylpyridinium-4-yl) porphyrin (TMetAlPyP4) with the poly(rA)poly(rU) and poly(rI)poly(rC) RNA duplexes between 18 and 45 degrees C by employing circular dichroism, light absorption, and fluorescence intensity spectroscopic measurements. Our results suggest that TEtOHPyP4 and TAlPyP4 intercalate into the poly(rA)poly(rU) and poly(rI)poly(rC) host duplexes, while TMetAlPyP4 associates with these RNA duplexes by forming outside-bound, self-stacked aggregates. We used our temperature-dependent absorption titration data to determine the binding constants and stoichiometry for each porphyrin-RNA binding event studied in this work. From the temperature dependences of the binding constants, we calculated the binding free energies, DeltaG(b), enthalpies, DeltaH(b), and entropies, DeltaS(b). For each RNA duplex, the binding enthalpy, DeltaH(b), is the most favorable for TEtOHPyP4 (an intercalator) followed by TAlPyP4 (an intercalator) and TMetAlPyP4 (an outside binder). On the other hand, for each duplex, external self-stacking of TMetAlPyP4 produces the most favorable change in entropy, DeltaS(b), followed by the intercalators TAlPyP4 and TEtOHPyP4. Thus, our results suggest that the thermodynamic profile of porphyrin-RNA binding may correlate with the binding mode. This correlation reflects the differential nature of molecular forces that stabilize/destabilize the two modes of binding-intercalation versus external self-stacking along the host duplex.     

On Extraction of Smooth Solutions of a Class of Almost Hypoelliptic Equations with Constant Power

A linear differential operator P(x, D) = P(x₁,... x _n , D₁,..., D _n ) = ∑_αγ_α(x)D^α with coefficients γ_α(x) defined in E ⁿ is called formally almost hypoelliptic in E ⁿ if all the derivatives D^ν_ξP(x, ξ) can be estimated by P(x, ξ), and the operator P(x, D) has uniformly constant power in Eⁿ. In the present paper, we prove that if P(x, D) is a formally almost hypoelliptic operator, then all solutions of equation P(x, D)u = 0, which together with some of their derivatives are square integrable with a specified exponential weight, are infinitely differentiable functions.     

Synthesis of dichloromethyl-substituted salicylates and pyran-4-ones by cyclocondensation of 1,3-bis(silyloxy)-1,3-butadienes with 1,1-dimethoxy-4,4-dichlorobut-1-en-3-one: control of the C,C- and C,O-regioselectivity by the choice of Lewis acid

The TiCl₄-mediated formal [3+3] cyclocondensation of 1,3-bis(trimethylsilyloxy)-1,3-butadienes with 1,1-dimethoxy-4,4-dichlorobut-1-en-3-one afforded a variety of functionalized 6-dichloromethyl-4-methoxysalicylates with very good regioselectivity. Some of the products were transformed into 6-formyl-4-methoxysalicylates. The employment of Me₃SiOTf instead of TiCl₄ resulted in a change of the regioselectivity and in the formation of functionalized 2-(dichloromethyl)pyran-4-ones.     

A New Method for Continuous Solid-State Biaxial Orientation of Polymeric Films

A new laboratory-scale method for continuous solid-state biaxial deformation of polymer materials is introduced. The tabletop biaxial drawing tool utilizes a heated metal disc-like triangular mandrel, which allows for continuous solid-state biaxial deformation of a precursor polymer tube with a controlled drawing speed. The new biaxial drawing tool features two independent heating zones. The main mandrel sets the biaxial drawing temperature. In addition, directly after the mandrel, an annealing unit with a separate heating zone is added for better control of important process parameters, such as post-relaxation and strain-induced crystallization. As such, the new biaxial drawing tool is a tabletop analogue of the industrial triple-bubble process. Finally, a detailed theoretical model describing the deformation field and the forces needed to perform biaxial drawing as a function of the biaxial drawing ratio is presented and compared to experimental values, using isotactic polypropylene as model material. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 352-362     

Shear wave propagation in periodic phononic/photonic piezoelectric medium

Coupled electro-elastic SH waves propagating oblique to the lamination of a one dimensional piezoelectric periodic structure are considered in the framework of the full system of Maxwell’s electrodynamic equations. The dispersion equation has been obtained and numerical analyses carried out for two kinds of composites both consisting of two different piezoelectric materials. The results demonstrate the significant effect of piezoelectricity on the widths of band gaps at acoustic frequencies and confirm that it does not affect the band gaps at optical frequencies.     

Synthesis of Novel 2‐Amino‐(2‐thioxo‐3‐alkyl‐4‐methyl‐3H‐thiazol‐5‐yl)‐[1,3,4]thiadiazole Derivatives and Their Growth Stimulant Activity

On the base of synthesized 2‐amino and 2‐ethylamino‐(2‐thioxo‐3‐alkyl‐4‐methyl‐3H‐thiazol‐5‐yl)‐[1,3,4]thiadiazoles, their alkyl, acetyl, and alkylacetylamino derivatives are obtained. The alkylation of 2‐ethylamino derivatives can occur at both exo and endo nitrogen atoms of amidine group, and the acetylation takes place exclusively at the exocyclic nitrogen atom. At acetylation of 2‐amino‐[1,3,4]thiadiazoles, only exo substitution is observed. At the further alkylation of these products, a mixture of exo‐ and endo‐substituted forms is obtained. At preliminary screening, the synthesized compounds have shown expressed growth stimulant properties. The activity of the most active derivatives was in the range of 65–100%, compared with that of heteroauxin.     

Synthesis and fungicidal activity of novel 1,3‐disubstituted 1H‐diazirine derivatives

A convenient method for synthesis of novel 1‐[pyrimidinyl], 1‐[1,3,5‐triazin‐2‐carbonyl], and 1‐[thiazol‐5‐carbonyl] derivatives of 3‐thioxo‐diaziridine 1 , 3 , 5 , and 7 from corresponding hydrazides, CS2, and KOH is elaborated. The highest reaction yield was observed when these initial reagents were taken in molar ratio of 1:1.7:2.0, respectively. By alkylation of compounds 1 , 3 , 5 , and 7 that proceeds exclusively at sulfur atom, the 3‐sulfanyl derivatives of 1‐[pyrimidinyl]‐, 1‐[1,3,5‐triazin‐2‐carbonyl]‐, and 1‐[thiazol‐5‐carbonyl]‐diazirines 2 , 4 , 6 , and 8 were formed. The structures of synthesized compounds were confirmed by proton and carbon nuclear magnetic resonance (NMR), mass spectra (MS), and elemental analysis. The fungicidal activities of S‐substituted derivatives were studied. Data of preliminary biological tests testify that these compounds can be of interest in search for new fungicides. J. Heterocyclic Chem., (2010).     

Extraction of smooth solutions of a class of regular equations in a rectangle

This work is devoted to the study of two-dimensional, regular, almost hypoelliptic operators P(D) = P(D ₂, D ₂) with regular Newton polyhedrons. It is proved that all generalized (weak) solutions of the equation P(D)u = f from a several weighted Sobolev space are infinitely differentiable functions in the rectangle {x ∈ E ²: −a < x ₁ < a, −b < x ₂ < b} in the variable x ₂, in which the function f is infinitely differentiable.     

Shear Bloch waves and coupled phonon–polariton in periodic piezoelectric waveguides

Coupled electro-elastic SH waves propagating in a periodic piezoelectric finite-width waveguide are considered in the framework of the full system of Maxwell’s electrodynamic equations. We investigate Bloch–Floquet waves under homogeneous or alternating boundary conditions for the elastic and electromagnetic fields along the guide walls. Zero frequency stop bands, trapped modes as well as some anomalous features due to piezoelectricity are identified. For mixed boundary conditions, by modulating the ratio of the length of the unit cell to the width of the waveguide, the minimum widths of the stop bands can be moved to the middle of the Brillouin zone. The dispersion equation has been investigated also for phonon–polariton band gaps. It is shown that for waveguides at acoustic frequencies, acousto-optic coupling gives rise to polariton behavior at wavelengths much larger than the length of the unit cell but at optical frequencies polariton resonance occurs at wavelengths comparable with the period of the waveguide.