Propionic Anhydride Modification of Cellulosic Kenaf Fibre Enhancement with Bionanocarbon in Nanobiocomposites

The use of chemical modification of cellulosic fibre is applied in order to increase the hydrophobicity, hence improving the compatibility between the fibre and matrix bonding. In this study, the effect of propionic anhydride modification of kenaf fibre was investigated to determine the role of bionanocarbon from oil palm shell agricultural wastes in the improvement of the functional properties of bionanocomposites. The vinyl esters reinforced with unmodified and propionic anhydride modified kenaf fibres bio nanocomposites were prepared using 0, 1, 3, 5 wt% of bio-nanocarbon. Characterisation of the fabricated bionanocomposite was carried out using FESEM, TEM, FT-IR and TGA to investigate the morphological analysis, surface properties, functional and thermal analyses, respectively. Mechanical performance of bionanocomposites was evaluated according to standard methods. The chemical modification of cellulosic fibre with the incorporation of bionanocarbon in the matrix exhibited high enhancement of the tensile, flexural, and impact strengths, for approximately 63.91%, 49.61% and 54.82%, respectively. The morphological, structural and functional analyses revealed that better compatibility of the modified fibre–matrix interaction was achieved at 3% bionanocarbon loading, which indicated improved properties of the bionanocomposite. The nanocomposites exhibited high degradation temperature which signified good thermal stability properties. The improved properties of the bionanocomposite were attributed to the effect of the surface modification and bionanocarbon enhancement of the fibre–matrix networks.

Alkylated albumin-derived dipeptide C(-HETE)P derivatized by propionic anhydride as a biomarker for the verification of poisoning with sulfur mustard

Sulfur mustard (SM) is a banned chemical warfare agent recently used in the Syrian Arab Republic conflict causing erythema and blisters characterized by complicated and delayed wound healing. For medical and legal reasons, the proof of exposure to SM is of high toxicological and forensic relevance. SM reacts with endogenous human serum albumin (HSA adducts) alkylating the thiol group of the cysteine residue C34, thus causing the addition of the hydroxyethylthioethyl (HETE) moiety. Following proteolysis with pronase, the biomarker dipeptide C(-HETE)P is produced. To expand the possibilities for verification of exposure, we herein introduce a novel biomarker produced from that alkylated dipeptide by derivatization with propionic anhydride inducing the selective propionylation of the N-terminus yielding PA-C(-HETE)P. Quantitative derivatization is carried out at room temperature in aqueous buffer within 10 s. The biomarker was found to be stable in the autosampler at 15 °C for at least 24 h, thus documenting its suitability even for larger sets of samples. Selective and sensitive detection is done by micro liquid chromatography-electrospray ionization tandem-mass spectrometry (μLC-ESI MS/MS) operating in the selected reaction monitoring (SRM) mode detecting product ions of the single protonated PA-C(-HETE)P (m/z 379.1) at m/z 116.1, m/z 137.0, and m/z 105.0. The lower limit of detection corresponds to 32 nM SM in plasma in vitro and the limit of identification to 160 nM. The applicability to real exposure scenarios was proven by analyzing samples from the Middle East confirming poisoning with SM. Graphical abstract

Effects of Acid-Anhydride-Modified Cellulose Nanofiber on Poly(Lactic Acid) Composite Films

In this study, we investigated the effect of the addition of cellulose nanofiber (CNF) fillers on the performance of poly(lactic acid) (PLA). Modification of the hydroxyl group of cellulose to the acyl group by acid anhydrides changed the compatibility of the CNF with PLA. CNF was modified by acetic anhydride, propionic anhydride, and butyric anhydride to form surface-modified acetylated CNF (CNFa), propionylated CNF (CNFp), and butyrylated CNF (CNFb), respectively, to improve the compatibility with the PLA matrix. The effects of the different acid anhydrides were compared based on their rates of reaction in the acylation process. PLA with modified cellulose nanofiber fillers formed smoother surfaces with better transparency, mechanical, and wettability properties compared with the PLA/CNF composite film. The effects of CNFa, CNFp, and CNFb on the PLA matrix were compared, and it was found that CNFp was the best filler for PLA.

Synthesis and Heterocyclization of 4-Hydroxy-3 - ((2-hydroxy-4,4-dimethyl-6-oxocyclohex1-en-1-yl) (aryl) methyl) -2H-chromen-2-ones

The possibility of obtaining asymmetric 1,5-diketones based on 4-hydroxy-2H-chromen-2-one and dimedone by three-component condensation in the presence of L-proline as a catalyst is shown. As a result, a series of 4-hydroxy3 - ((2-hydroxy-4,4-dimethyl-6-oxocyclohex1-en-1-yl) (aryl) methyl) -2H-chromen-2-ones was obtained with a yield of 25 up to 73%. The study revealed that the highest yield was observed for compounds containing fragments of ortho-substituted aldehydes capable of forming a hydrogen bond. For meta- and para-substituted – the lowest yield was observed. In the case of ortho-substitution this can be probably explained due to the stabilization of the intermediate complex by two intramolecular hydrogen bonds, which makes it possible to selectively obtain only one final product – 4-hydroxy-3 -((2-hydroxy4,4-dimethyl-6-oxocyclohex-1- en-1-yl) (aryl) methyl) -2Hchromen-2-one. The structure of the obtained products was confirmed by 1 H, 13C NMR, HSQC, HMBC spectroscopy. Considering the 1,5-diketone fragment for the above-described compounds, the possibility of their O-heterocyclization by propionic anhydride was suggested. Boiling 4-hydroxy-3 - ((2-hydroxy-4,4-dimethyl-6-oxocyclohex-1-en-1-yl) (aryl) methyl) -2Hchromen-2-ones in anhydride medium for an hour resulted in obtaining a series of 7- (aryl) -10,10-dimethyl-7,9,10,11-tetrahydro-6H, 8H-chromeno [4,3-b] chromene-6,8-diones. Their structure was also confirmed by 1 H, 13C NMR, HSQC, HMBC spectroscopy.

The Effect of Fiber Chemical Treatment on Chemical Resistance Behavior of Jute Polyethylene Composites for Storage Tank Application

The jute polyethylene composites were developed using the hot-press technique with different fiber weight ratios. Due to the hydrophilic nature of fiber, it exhibited poor interfacial interaction to hydrophobic polymer matrix. In order to enhance the interfacial interaction between fiber and polymer, the benzene diazonium salt (BDS), propionic anhydride (PA), and 3-isocyanatopropyl triethoxysilane (silane) treated jute were used for the manufacturing of composites in this study. The chemical resistance tests of prepared composites were performed in order to probe whether these are resistant to various chemicals such as: acids, alkalis, and solvents. The effect of chemical treatments of the composites have been investigated. It was observed that the fabricated composites were resistant to all chemicals except carbon tetrachloride. The treated jute composites showed higher chemical resistance than raw jute composite and silane treated jute composite yield the highest resistance which can be suggested for making the water and chemical storage tanks.