Biodegradable Polyurethanes from Plant Components

Abstract

Polyurethane (PU) sheets and foams having plant components in their network were prepared by using the following procedure. Polyethylene glycol (PEG) was mixed with one of the following; molasses, lignin, woodmeal, or coffee grounds. The mixture obtained was reacted with diphenylmethane diisocyanate (MDI) at room temperature, and precured PUs were prepared. The precured PUs were heat-pressed and PU sheets were obtained. In order to make PU foam, the above mixture was reacted with MDI after the addition of plasticizer, surfactant (silicone oil), catalyst (di-n-butyltin dilaurate), and droplets of water under vigorous stirring. The glass transition temperature, tensile and compression strengths, and Young's modulus of the PU sheets and foams increased with an increasing amount of plant components. This suggests that saccharide and lignin residues act as hard segments in PUs. It was found that the PUs obtained were biodegradable in soil. The rate of biodegradation of the PUs derived from molasses and coffee grounds was between that of cryptomeria (Cryptomeria japonica) and beech (Fagus sieboldi).     

Synthesis of poly(ethylene glycol)‐based hydrogels and their swelling/shrinking response to molecular recognition

To synthesize the novel molecular‐ and pH‐stimulus‐responsive hydrogel, we prepared poly(ethylene glycol)‐based hydrogel containing ionic groups. We evaluated the fundamental swelling/shrinking properties of the hydrogels synthesized by various conditions. Decreasing the molecular weight of a crosslinker provided the increasing of the equilibrium swelling ratio. Also, the equilibrium swelling ratio was changed by the introduction of functional ionic monomers and its compositions. Furthermore, the swelling/shrinking behaviors of the hydrogels were affected by the environmental condition of aqueous solution, in fact the hydrogels were considerably shrunk (to one‐fifth volume) using a di‐ionic solute in the aqueous solution through the ionic interactions between the hydrogel and the solutes. Additionally, the specific shrinking to diamine compounds was also observed in response to pH change. These results clearly show the swelling/shrinking responsibility of the hydrogels toward the molecular recognitions and its pH conditions. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3153–3158     

Synthesis of fluorine‐containing star‐shaped poly(vinyl ether)s via arm‐linking reactions in living cationic polymerization

Various types of fluorine‐containing star‐shaped poly(vinyl ether)s were successfully synthesized by crosslinking reactions of living polymers based on living cationic polymerization. Star polymers with fluorinated arm chains were prepared by the reaction between a divinyl ether and living poly(vinyl ether)s with fluorine groups (C₄F₉, C₆F₁₃, and C₈F₁₇) at the side chain using cationogen/Et_1.5AlCl_1.5 in a fluorinated solvent (dichloropentafluoropropanes), giving star‐shaped fluorinated polymers in high yields with a relatively narrow molecular weight distribution. The concentration of living polymers for the crosslinking reaction and the molar feed ratio of a bifunctional vinyl ether to living polymers affected the yield and molecular weight of the star polymers. Star polymers with block arms were prepared by a linking reaction of living block copolymers of a fluorinated segment and a nonfluorinated segment. Heteroarm star‐shaped polymers containing two‐ or three‐arm species were synthesized using a mixture of different living polymer species for the reaction with a bifunctional vinyl ether. The obtained polymers underwent temperature‐induced solubility transitions in various organic solvents, and their concentrated solutions underwent sol–gel transitions, based on the solubility transition of a thermoresponsive fluorinated segment. Furthermore, a slight amount of fluorine groups were shown to be effective for physical gelation when those were located at the arm ends of a star polymer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Efficient Synthesis of Polycyclic γ-Lactams by Catalytic Carbonylation of Ene-Imines via Nickelacycle Intermediates

The nickel(0)-catalyzed carbonylative cycloaddition of 1,5- and 1,6-ene-imines with carbon monoxide (CO) is reported. Key to this reaction is the efficient regeneration of the catalytically active nickel(0) species from nickel carbonyl complexes such as [Ni(CO)₃L]. A variety of tri- and tetracyclic γ-lactams were thus prepared in excellent yields with 100 % atom efficiency. Preliminary results on asymmetric derivatives promise potential in the synthesis of enantioenriched polycyclic γ-lactams.     

Synthesis and properties of cross-linkable DNA duplex using 4-amino-2-oxo-6-vinyl-1,3,5-triazine

We synthesized the DNA oligonucleotide containing a new cross-linkable 4-amino-2-oxo-6-vinyltriazine (AOVT) nucleobase analogue (Et-AOVT) and evaluated these properties. Our results of the cross-link assay and thermal denaturing assay of duplexes containing AOVT demonstrated that the additional aza of AOVT has an impact on the duplex stability and crosslink properties. Our data suggests that the additional 5-aza of AOVT is involved in the hydrogen bonding with the complementary guanine, and this hydrogen bonding system successfully flipped the reactive vinyl group out to the major groove of the duplex demonstrating a new paradigm of a “cross-linkable duplex”.     

Phytochemical Analysis and Habitat Suitability Mapping of Glycyrrhiza glabra L. Collected in the Hatay Region of Turkey

The growth and quality of licorice depend on various environmental factors, including the local climate and soil properties; therefore, its cultivation is often unsuccessful. The current study investigated the key factors that affect the contents of bioactive compounds of Glycyrrhiza glabra L. root and estimated suitable growth zones from collection sites in the Hatay region of Turkey. The contents of three bioactive compounds (glycyrrhizic acid, glabridin, and liquiritin), soil factors (pH, soil bearing capacity, and moisture content), and geographical information (slope, aspect, curvature, elevation, and hillshade) were measured. Meteorological data (temperature and precipitation) were also obtained. An analysis of variance (ANOVA) and multivariate analysis of variance (MANOVA) were performed on the data. The soil bearing capacity, moisture content, slope, aspect, curvature, and elevation of the study area showed statistically significant effects on the glycyrrhizic acid and liquiritin contents. A habitat suitability zone map was generated using a GIS-based frequency ratio (FR) model with spatial correlations to the soil, topographical, and meteorological data. The final map categorized the study area into four zones: very high (15.14%), high (31.50%), moderate (40.25%), and low suitability (13.11%). High suitability zones are recommended for further investigation and future cultivation of G. glabra.