ABSTRACT
Starch acetates and starch butyrates with degree of substitution (DS) in the range of 0.06-1.54 were prepared by a simple direct solvent-free organocatalytic methodology of starch acylation. The starch esters synthesized have important applications in the food and pharmaceutical industries, among others. The acylation methodology used involves a non-toxic biobased α-hydroxycarboxylic acid as catalyst, and proceeds with high efficiency in absence of solvents. The effect of reaction time on the advance of starch modification was studied as a simple way to control the level of substitution achieved, when all other reaction parameters were kept constant. Starch esters were characterized by means of Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and X-ray diffraction (XRD). FTIR spectroscopy qualitatively confirmed the esterification of starch by the appearance of bands which are associated with esters groups. Scanning electron microscopy showed that the granular structure of the polysaccharide was preserved upon acylation, although acylated granules had rougher surfaces; and wrinkles, grooves and deformed zones appeared in some granules at high DS. Thermogravimetric analysis showed a gradual reduction in the water content of acylated starches, as well as noticeable changes in their thermal properties at increasing DS. X-ray diffraction analysis showed that the acetylation treatment led to lower crystallinity at increasing DS, although characteristic corn starch A-type patterns could be identified even at the highest DS achieved (DS=1.23). Specific bands and weight losses derived from FTIR and TGA data could be very well correlated with the substitution degree achieved in acetylated starches at DS lower/equal than 0.6. The organocatalytic methodology described for the synthesis of starch acetates and butyrates has the potential to be easily extended to the synthesis of other starch esters using a variety of anhydrides or carboxylic acids as acylating agents.
Subject(s)
Starch/chemistry , Starch/chemical synthesis , Acylation , Catalysis , Chemistry Techniques, Synthetic , EstersABSTRACT
Cellulose nanoparticles (i.e. cellulose elements having at least one dimension in the 1-100 nm range) have received increasing attention during the last decade. This is not only evident in academic articles, but it is also manifested by the increasing number of nanocellulose patents that are published every year. In the current review, nanocellulose patents are reviewed using specific software which provides valuable information on the annual number of patents that have been published throughout the years, main patent owners, most prolific inventors, and patents on the field that have received more citations. Patent statistics on rod-like cellulose nanoparticles extracted from plants by acid hydrolysis (nanocrystals), mechanical treatment leading to microfibrillated cellulose (MFC), and microbially produced nanofibrils (bacterial cellulose, BC) are analyzed in detail. The aim of the current review is to provide researchers with patent information which may help them in visualizing the evolution of nanocellulose technology, both as a whole and also divided among the different nanosized particles that are currently the subject of outstanding scientific attention. Then, patents are not only analyzed by their content, but also by global statistics which will reveal the moment at which different cellulose nanoparticles technologies achieved a breakthrough, the relative interest received by different nanocellulose particles throughout the years, the companies that have been most interested in this technology, the most prolific inventors, and the patents that have had more influence in further developments. It is expected that the results showing the explosion that nanocellulose technology is experiencing in current days will still bring more research on the topic and contribute to the expansion of nanocellulosics applications.