Reductive Methylation of Homogeneous Primary β-Lauryl/myristyl 7/3 Polyethyleneoxy n = 3–18 Ethylamines under Phase-Transfer Catalysis Conditions

Homogeneous tertiary N,N-dimethyl-N-β-lauryl/myristyl 7/3 polyethyleneoxy n = 3–18 ethylamines, LM(EO)nAT, are niche intermediates in the synthesis of homogeneous N-alkyl (C1–C18)-N,N-dimethyl-N-β-lauryl/myristyl 7/3 polyethyleneoxy n = 3–18 ethylammonium chlorides (unitary degree of oligomerization of ethylene oxide in the polyoxyethylene chain). This paper synthetically presents the dependence of the reductive methylation yields of homogeneous primary β-lauryl/myristyl 7/3 polyethyleneoxy n = 3–18 ethylamines, LM(EO)nAP, on the reaction time (10–90 min), the temperature (70 °C), the molar ratio formic aldehyde /LM(EO)nAP (1.1/1–2.5/1), the molar ratio HCOOH/LM(EO)nAP (5/1), the degree of oligomerization of ethylene oxide in the homogeneous polyoxyethylene chain in the 3,6,9,12,18 series, and the structure of the phase-transfer catalysts. The steric effects of hydrophobic groups CH3 and C18H37 grafted onto the ammonium function, and the micellar phenomena in the vicinity of their critical micellar concentration, directly proportional to the homogeneous degree of oligomerization, were highlighted. In all cases, a steady increase in reductive methylation yields was observed, with even quantitative values obtained. The high purity of the homologous series LM(EO)nAT will allow their personalization as reference structures for the study of the evolution of basic colloidal characteristics useful in forecasting technological applications. LM(EO)nAP were obtained either by direct amidoethylation (nucleophilic addition under basic catalysis of homogeneous lauryl/myristyl 7/3 polyethoxylated n = 3, 6, 9, 12, 18 alcohols, LM(EO)nOH, to acrylamide monomer) or by cyanoethylation of LM(EO)nOH under basic catalysis at 25–50 °C, in the presence of Fe2+ cations as oligomerization/polymerization inhibitor, followed by partial acid hydrolysis of homogeneous β-alkyl (C12H25/C14H29) 7/3 polyethyleneoxy n = 3, 6, 9, 12, 18 propionitriles, LM(EO)nPN, to β-alkyl (C12H25/C14H29) 7/3 polyethyleneoxy n = 3, 6, 9, 12, 18 propionamides, LM(EO)nPD, which led to LM(EO)nAP by Hoffmann degradation. Homogeneous higher tertiary polyetheramines LM(EO)nAT were structurally characterized.

Degree-Based Topological Indices of Polysaccharides: Amylose and Blue Starch-Iodine Complex

Starch is a polymer of glucose where alpha-linkages are associated with glucopyranose units. It comprises a mixture of amylose and amylopectin. Furthermore, amylose is a linear chain of hundreds of glucose molecules. Starches are not allowed to be dissolved in water. They can be digested by breaking down alpha bonds (glycosidic bonds). Its cyclic degradation products, called cyclodextrins, are the best role models for amylose. They can be considered simple turns of the amylose propeller that has imploded into a circular path. Both humans and animals have amylases, which allow them to digest starches. The important sources of starch include potatoes, rice, wheat, and maize for human consumption. The production of starches is how plants store glucose. The blue colour of starch produced by an iodine solution or iodine reaction is used for its identification. Polysaccharides with a reduced degree of polymerization, known as dextrins, are produced in the starch’s partial acid hydrolysis. Complete hydrolysis leads to glucose. In this article, we compute the topological properties: Zagreb index M 1 Γ and M 2 Γ , Randić index R α Γ for α = − 1 / 2 , − 1 , 1 / 2 , 1 , atom-bond connectivity index ABC Γ , geometric-arithmetic index GA Γ , fourth atom-bond connectivity index ABC 4 Γ , fifth geometric-arithmetic index GA 5 Γ , and degree-based topological indices of a graph Γ representing polysaccharides, namely, amylose and blue starch-iodine complex. In the end, we compare these indices and depict their graphic behavior.

Influence of Partial Acid Hydrolysis on Size, Dispersity, Monosaccharide Composition, and Conformation of Linearly-Branched Water-Soluble Polysaccharides

The effect of partial acid hydrolysis on the physical and chemical properties of galactomannan, arabinoxylan, and xyloglucan was investigated. Polysaccharides were treated at 50 °C with hydrochloric acid for 3–48 h. Portions of isopropanol (i-PrOH) were added sequentially to the hydrolyzates, resulting in fractions that were collected by centrifugation. As expected, a significant reduction of weight-average molecular weight (Mw) was observed with increasing hydrolysis time. Fractional precipitation was successfully applied to collect at least one polymer fraction with dispersity (Đ) close to one for each polysaccharide. The monosaccharide composition analysis showed that the partial hydrolysis usually lowered the relative amount of side chains, with the exception of galactomannan, where the composition remained largely unaffected. Estimation of the polymer conformation in solution, through evaluation of the Mark-Houwink parameter coefficient (α), confirmed that acid hydrolysis influenced the polysaccharides’ conformation. It was demonstrated that acid treatment in dilute solution followed by fractional isopropanol precipitation is a method, extendible to a variety of polysaccharides, to obtain materials of decreased molecular weight and low dispersity with slightly altered overall composition and conformation.

THE INFLUENCE OF SURFACE DESTRUCTION ON THE HYDROPHILICITY AND ABILITY TO FORM CONNEC-TIONS OF THE CELLULOSE FIBERS

When using cellulose fibers to produce paper, the main role is played by the state of the surface of the fiber and its ability to adhesive-cohesive interaction. The main indicators characterizing the surface of the fiber are development and roughness, chemical heterogeneity, depending on the presence of various functional groups, as well as structural heterogeneity of the surface layers, leading to the formation of a stronger bond between the fibers. The surface modification of the fiber was carried out by partial acid hydrolysis. The study is aimed at optimizing hydrolysis, choosing methods for its control, obtaining physicochemical and physicomechanical characteristics of partially hydrolyzed cellulose, and increasing the ability to bind cellulose fiber. A method has been developed for producing modified cellulose with improved adhesion-cohesive properties by surface destruction of wet cellulose fibers during hydrolysis. The patterns of activation of the surface properties of cellulose fibers are obtained. The effect of partial acid hydrolysis on the development of the surface of the fiber in the absence of "wet" grinding with water shortage is shown. The effect of short chains and reducing carbonyl groups of cellulose macromolecules on the binding capacity of modified cellulose has been established. The optimal content of short chains of cellulose macromolecules, which is 12%. Such a content of short chains of modified fibers by acid hydrolysis was detected at a temperature of 363 K and an exposure time of 40 s; under these optimal conditions, the strength of the experimental castings increases by 70%.

Removal of Arabinose Substituents from Corn Pericarp Arabinoxylan

Partial acid hydrolysis of corn pericarp arabinoxylan (arabinose/xylose (A/X) ratio 0.35 and mean molecular weight of 53.6 × 103) was carried out at pH 1.0 for 1 ~ 6 h at 37 ~ 57 °C to remove arabinose substituents. The removal of arabinose could be described by regression analysis with the method of least squares. Following the regression profile, three kinds of desubstituted arabinoxylans having A/X ratios of 0.25, 0.12 and 0.03 with mean molecular weight values of 37.3 × 103, 15.6 × 103 and 7.2 × 103, respectively, could be prepared. All corn pericarp arabinoxylans were in the amorphous state and the film formability of the native state was lost after the partial acid hydrolysis.