ABSTRACT
This work demonstrates that acetylated maize starches (AMS) with varied degree of substitution (DS, 0.26-2.63) was synthesized in ionic liquids (ILs) (imidazolium chloride, imidazolium carboxylate and choline carboxylate) at 85 °C without catalyst. The DS of AMS and reaction efficiency increased with decreasing alkyl chain length of cations or anions, while decreased as the choline cation replaced the imidazolium cation and the chloride anion replaced the acetate anion. The AMS synthesized in imidazolium-based ILs exhibited much higher hydrophobicity and thermal stability than the native starch. Rheological properties of ILs and ATR-FTIR analysis of acetic anhydride/ILs mixtures indicated that a shorter alkyl side chain or the combination of an imidazolium cation and an acetate anion gave ILs lower viscosities and weaker interactions between acetic anhydride molecules, which favored the acetylation of starch. These findings provide insights into the design of green processes to modify starch and the application of acetylated starch.
Subject(s)
Acetic Anhydrides/chemical synthesis , Ionic Liquids , Anions , Carboxylic Acids/chemistry , Cations , Choline/chemistry , Ionic Liquids/chemistry , Starch , Zea maysABSTRACT
A retrospective cohort mortality study was conducted at a chemical plant producing acetic acid and acetic anhydride, two chemicals essential in the synthesis of cellulose triacetate fiber. Previously, we reported excess mortality from biliary tract and prostate cancers among workers in cellulose triacetate fiber manufacturing plants. In the present investigation, an excess of prostate cancer (SMR = 330.4; 95% confidence interval = 121.3-719.1) was observed among former chemical plant workers, some of whom had been exposed to both acetic acid and acetic anhydride. These apparent increases in mortality are difficult to interpret biologically, particularly in light of recent suggestions concerning the role of endocrine factors. Additional work is planned to more fully characterize potential occupational exposures that might explain the etiology of prostate cancer.
Subject(s)
Chemical Industry , Prostatic Neoplasms/mortality , Acetic Acid/chemical synthesis , Acetic Anhydrides/chemical synthesis , Age Factors , Bronchial Neoplasms/mortality , Cellulose/analogs & derivatives , Cellulose/chemical synthesis , Cohort Studies , Confidence Intervals , Female , Follow-Up Studies , Heart Diseases/mortality , Humans , Lung Diseases/mortality , Lung Neoplasms/mortality , Male , Middle Aged , Neoplasms/mortality , Occupational Exposure , Prostatic Neoplasms/etiology , Racial Groups , Retrospective Studies , Sex Factors , Texas/epidemiology , Tracheal Neoplasms/mortalityABSTRACT
Isopropoxyacetic anhydride was successfully used for protection of exoaminofunctions of 2'-deoxyadenosine, -guanosine and -cytidine. N-isopropoxyacetylated nucleosides are stable under the conditions of the synthesis of oligodeoxyribonucleotides on the solid support. Removal of N-isopropoxyacetyl is much faster than that of commonly used benzoyl or isobutyryl groups viz. it is completed within the operation of cleavage of the oligodeoxyribonucleotide from the solid support. This observation enabled synthesis of -OCH2CH3 and -OCH2CF3 triesters, which hydrolyse partially or completely when standard deprotection conditions are applied.
