Plant polysaccharides are widely found in nature and have a variety of biological activities, including immunomodulatory, antioxidative, and antitumoral. Due to their low toxicity and easy absorption, they are widely used in the health food and pharmaceutical industries. However, low activity hinders the wide application. Chemical modification is an important method to improve plant polysaccharides’ physical and chemical properties. Through chemical modification, the antioxidant and immunomodulatory abilities of polysaccharides were significantly improved. Some polysaccharides with poor water solubility also significantly improved their water solubility after modification. Chemical modification of plant polysaccharides has become an important research direction. Research on the modification of plant polysaccharides is currently increasing, but a review of the various modification studies is absent. This paper reviews the research progress of chemical modification (sulfation, phosphorylation, acetylation, selenization, and carboxymethylation modification) of land plant polysaccharides (excluding marine plant polysaccharides and fungi plant polysaccharides) during the period of January 2012–June 2022, including the preparation, characterization, and biological activity of modified polysaccharides. This study will provide a basis for the deep application of land plant polysaccharides in food, nutraceuticals, and pharmaceuticals.

Alfalfa polysaccharides (AP) receive wide attention in the field of medicine, because of their anti-inflammatory property. However, AP has high molecular weight and poor water solubility, resulting in low biological activity. We wanted to obtain highly bioactive alfalfa polysaccharides for further research. Herein, we successfully synthesized highly substituted sulfated alfalfa polysaccharides (SAP) via the chlorosulfonic acid (CSA)-pyridine (Pyr) method, which was optimized using response surface methodology (RSM). Under the best reaction conditions, that is, the reaction temperature, time, and ratio of CSA to Pyr being 55 °C, 2.25 h, and 1.5:1, respectively, the maximum degree of substitution of SAP can reach up to 0.724. Fourier transform infrared spectroscopy also confirmed the existence of sulfonic acid groups on SAP. Despite the increased average molecular weight of SAP, its water solubility is improved, which is beneficial for its biological activity. Further in vitro results showed that SAP exhibited better antioxidant activity and antibacterial ability than AP. Besides, the former can efficiently enhance the viability of oxidatively stressed intestinal epithelial cells compared with the latter. Furthermore, SAP has the potential to inhibit obesity. It is concluded that sulfation modification could improve the antioxidant, antibacterial, bovine intestinal epithelial cells’ proliferation-promoting, and the obesity inhibition abilities of AP. The improvement of AP biological activity may provide references for the utilization of plant extracts that have weaker biological activity.

Sulfated alfalfa polysaccharides (SAPs) as derivatives of alfalfa polysaccharides (APs) showed better in vitro antioxidant activity and potential obesity inhibition.

Alfalfa (Medicago sativa L.) saponins (AS), primarily pentacyclic triterpenoids, may reduce methane emissions from goats (Capra hircus L.). This study evaluated the methane-suppressing potential of Aspergillus niger β-glucosidase-modified AS using in vitro rumen fermentation (0.10 mg/mL inoculum, 24 h incubation, gas chromatography detection). Among the 21 alfalfa cultivars, Pegasis (fall dormancy 9) exhibited the highest antioxidant efficacy (half maximum effective concentration 2.13 mg/mL) and the lowest ferric-reducing activity (0.32 μM Fe²⁺/g) (p < 0.05). Fresh/silage AS reduced methane proportions to 4.50–5.21% of total gas, while enzymatic biotransformation further decreased it to 3.34–3.48% (p < 0.05). Methanogen abundance declined by 20.10–44.93%, and general anaerobic fungi declined by 34.22–44.66% compared to untreated AS (p < 0.05). Metabolomics linked methane suppression to six pathways, including zeatin biosynthesis (via nucleotide metabolites accumulation) and prolactin signaling pathway (via bioactive molecules downregulation), suggesting impaired methanogen energy metabolism and hydrogen flux redirection as mechanisms. Enzymatic AS also enhanced volatile fatty acid production, indicating improved fiber digestion. These in vitro findings demonstrate that enzyme-treated AS modulates rumen fermentation through dual methane mitigation and nutrient utilization enhancement, offering a sustainable feed additive strategy for livestock.