RESUMEN

Polymer networks were prepared by Steglich esterification using poly(sorbitol adipate) (PSA) and poly(sorbitol adipate)-graft-poly(ethylene glycol) mono methyl ether (PSA-g-mPEG12) copolymer. Utilizing multi-hydroxyl functionalities of PSA, poly(ethylene glycol) (PEG) was first grafted onto a PSA backbone. Then the cross-linking of PSA or PSA-g-mPEG12 was carried out with disuccinyl PEG of different molar masses (Suc-PEGn-Suc). Polymers were characterized through nuclear magnetic resonance (NMR) spectroscopy, gel permeation chromatography (GPC), and differential scanning calorimetry (DSC). The degree of swelling of networks was investigated through water (D2O) uptake studies, while for detailed examination of their structural dynamics, networks were studied using 13C magic angle spinning NMR (13C MAS NMR) spectroscopy, 1H double quantum NMR (1H DQ NMR) spectroscopy, and 1H pulsed field gradient NMR (1H PFG NMR) spectroscopy. These solid state NMR results revealed that the networks were composed of a two component structure, having different dipolar coupling constants. The diffusion of solvent molecules depended on the degree of swelling that was imparted to the network by the varying chain length of the PEG based cross-linking agent.

RESUMEN

Enzymatic polymerization is an environmentally benign process for the synthesis of biodegradable and biocompatible polymers. The regioselectivity of lipase B from Candida Antarctica (CAL-B) produces linear functional polyesters without protection-deprotection steps. In this work, two different methods for the enzymatic synthesis of functional polyesters based on renewable resources, as, e.g., glycerol, using CAL-B are outlined. Poly(glycerol adipate) was synthesized by enzymatic transesterification between glycerol and divinyl adipate or dimethyl adipate. Methods are also reported to graft poly(glycerol adipate) with different amounts of hydrophobic side chains (lauric, stearic, behenic, and oleic acids) and hydrophilic poly(ethylene glycol) side chains, respectively. The hydrophilicity or lipophilicity of grafted polyesters is well controlled by changing the degree of grafting of hydrophilic and hydrophobic side chains. The multiple grafted polyesters are characterized by NMR spectroscopy, differential scanning calorimetry, gel permeation chromatography, and X-ray diffraction. Furthermore, the self-assembly of the graft copolymers in water and their use as steric stabilizers for cubosomes are discussed. For this purpose mainly dynamic light scattering and small angle X-ray scattering have been employed.

Asunto(s)

Adipatos/metabolismo , Biocatálisis , Glicerol/metabolismo , Poliésteres/metabolismo , Rastreo Diferencial de Calorimetría , Cromatografía en Gel , Interacciones Hidrofóbicas e Hidrofílicas , Espectroscopía de Resonancia Magnética , Poliésteres/síntesis química , Polietilenglicoles , Polimerizacion , Difracción de Rayos X

RESUMEN

Biodegradable and hydrophilic functional polyesters were synthesized enzymatically using xylitol or d-sorbitol together with divinyl adipate and lipase B from Candida antartica (CAL-B). The resulting polyesters had pendant OH-groups from their sugar units which were esterified to different degrees with stearic acid chloride. The structure and the degrees of polymerization of the resulting graft copolymers based on poly(xylitol adipate) and poly(d-sorbitol adipate) were characterized by ¹H NMR spectroscopy and SEC. DSC, WAXS and SAXS measurements indicated that a phase separation between polymer backbone and stearoyl side chains occurred in the graft copolymers, and, additionally, the side chains were able to crystallize which resulted in the formation of a lamellar morphology. Additionally, nanoparticles of the graft copolymers in an aqueous environment were studied by DLS and negative stain TEM.

RESUMEN

In the title compound, C(12)H(13)NO(3)S, a saccharin derivative, the dihedral angle between the aromatic and isothia-zole rings is 2.91 (12)°. The planar 3,3-dimethyl-allyl group [maximum deviation = 0.0086 (16) Å] is oriented at dihedral angles of 71.86 (7) and 74.35 (7)° with respect to the aromatic and isothia-zole rings, respectively. In the crystal structure, weak inter-molecular C-H⋯O inter-actions link the mol-ecules into chains along the c axis. A weak C-H⋯π inter-action is also present.