Highly porous polymeric sponges for oil sorption

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Kinetic model for Ostwald's rule of stages with applications to Boc-diphenylalanine self-assembly

A kinetic model which describes Ostwald's rule of stages, during the process of crystal growth from solution, is reported here. Reaction equations for stages are given where the stages convert from one to another. The final stage reacts to release a portion of solute back into solution, while the remainder converts to the final equilibrium form. Additionally, a remnant of the solute that was not consumed by any of the transitional stages, ultimately is converted into the final product. This particular model was motivated by a recent report for Boc-diphenylalanine self-assembly where the dissolved peptide was observed to go through two polymorphic stages before reaching the equilibrium supramolecular assembly [A. Levin et al., Nat. Commun. 5, 5219, (2014)]. Kinetic data for the concentration of solute present during the process are listed in the above-mentioned report. We show here how the model, for , describes the time-dependent behavior of the solute decay during the growth process. After comparing the model to the experimental data, we are able to report values for all of the rate constants and propose a rule whereby the relative magnitudes of these constants can be used to predict whether a supersaturated substance will noticeably pass through transitional stages or simply convert from solute to the equilibrium solid form.     

Temperature effect on the microstructure and viscoelastic properties of aqueous micellar systems of sodium <Emphasis Type="Italic">N</Emphasis>-methyl-<Emphasis Type="Italic">N</Emphasis>-oleyl taurate

The quantitative characteristics of the temperature effect on the rheological properties of aqueous solutions of the anionic surfactant sodium methyl oleyl taurate (SMOT) are presented. An increase in the intensity of thermal motion of surfactant molecules on heating from 25 to 45 °С was shown to decrease the average contour length of SMOT micelles from 2 μm to 700 nm. The decrease in the length of cylindrical micelles is probably one of the main reasons for a substantial decrease in the viscosity of micellar solutions of the surfactant with temperature.     

Supramolecular catalytic systems based on 1, 4-diazabicyclo[2.2.2]octane,its alkylated quaternary derivatives,and lanthanum nitrate

Spectrophotometry was used to study the catalytic effects of the systems composed of N-monoand N, N-dialkylated 1, 4-diazabicyclo[2.2.2]octanes and lanthanum nitrate on the hydrolysis rate of O-alkyl O-4-nitrophenyl chloromethylphosphonates (Alk = Et, Buⁿ, and n-hexyl). The mechanism of action and efficiency of the catalytic system depend on the structure of the heterocycle, its propensity to aggregation and complexation with the lanthanum cation, and the relative content of the components in solution. The maximum catalytic effect (a ～115-fold increase in the hydrolysis rate constant) was achieved in micellar solutions of the cationic monoalkylated derivative of 1, 4-diazabicyclo[2.2.2]octane and lanthanum nitrate.

     

Polysaccharides of algae 67. Carrageenan from Pacific red alga Turnerella mertensiana (Gigartinales,Rhodophyta)

A sulfated galactan composed of nearly equimolar amounts of d-galactose, 3,6-anhydro-d-galactose, and sulfate was isolated from the red alga Turnerella mertensiana collected in the Sea of Japan. The structures of native polysaccharide and its alkaline modification products were studied by NMR spectroscopy. The polysaccharide molecules were shown to contain a linear carbohydrate chain consisting of alternating 3-linked β-d-galactopyranose 4-sulfate and 4-linked 3,6-anhydro-α-d-galactopyranose residues (known as к-carrageenan), which is typical of carrageenans, but the regularity of polymer structure is masked by the presence of some 3,6-anhydro-α-d-galactose 2-sulfate (ι-carrageenan units) and α-D-galactose 6-sulfate (µ-carrageenan units) instead of 3,6-anhydro-α-d-galactose. Upon addition of potassium chloride (up to 4%) to a solution of the native polysaccharide, about half of the substance transforms into gel. The gel-forming fraction is к-ι-µ-hybrid carrageenan with the ～65 : 15 : 20 ratio of к-, ι-, and µ-units. The non-gelling fraction contains the к-, ι-, and µ-units at the ratio of ～46 : 12 : 42. The gel-forming carrageenan product free of µ-units can be otained in ～30% yield (based on the dry biomass) by alkaline treatment of the alga prior to extraction of the polysaccharide.

     

Design of phosphonate analogs of short peptides by “click” chemistry

Methods were developed for the first time for the modification of the natural neuropeptides Ile–Gly–Leu and Leu–Gly–Leu simultaneously with the phosphonate moiety and the triazole ring or solely with the triazole ring by means of click chemistry. All of the peptidomimetics synthesized were isolated as a mixture of diastereomers and were characterized by spectroscopic methods.

     

Enthalpies of the Diels–Alder reactions of a series of dienes with tetracyanoethylene and 4-phenyl-1,2,4-triazoline-3,5-dione

Russian Chemical Bulletin - The enthalpies of the Diels–Alder reactions of twenty dienes with two active dienophiles, tetracyanoethylene and 4-phenyl-1,2,4-triazoline-3,5-dione, are compared,...