Background: Lenalidomide-based therapies are recommended as first-line treatment for multiple myeloma (MM) patients, regardless of the transplant eligibility. Resistance to lenalidomide is a clinical problem that urgently needs to be addressed. The expression of poly(ADP-ribose) polymerase 1 (PARP1) is abnormally high in a variety of tumor tissues including MM.
View Article and Find Full Text PDFCellulose serves as a sustainable biomaterial for a wide range of applications in biotechnology and materials science. While chemical and enzymatic glycan assembly methods have been developed to access modest quantities of synthetic cellulose for structure-property studies, chemical polymerization strategies for scalable and well-controlled syntheses of cellulose remain underdeveloped. Here, we report the synthesis of precision cellulose via living cationic ring-opening polymerization (CROP) of glucose 1,2,4-orthopivalates.
View Article and Find Full Text PDFCyclic ketene acetals (CKAs) are among the most well-studied monomers for radical ring-opening polymerization (rROP). However, ring-retaining side reactions and low reactivities in homopolymerization and copolymerization remain significant challenges for the existing CKAs. Here, we report that a class of monosaccharide CKAs can be facilely prepared from a short and scalable synthetic route and can undergo quantitative, regiospecific, and stereoselective rROP.
View Article and Find Full Text PDFThe composition, sequence, length and type of glycosidic linkage of polysaccharides profoundly affect their biological and physical properties. However, investigation of the structure-function relationship of polysaccharides is hampered by difficulties in accessing well-defined polysaccharides in sufficient quantities. Here we report a chemical approach to precision polysaccharides with native glycosidic linkages via living cationic ring-opening polymerization of 1,6-anhydrosugars.
View Article and Find Full Text PDFBackground: Colorectal cancer (CRC) is the third most common malignancy. Immunoinvasion of tumor microenvironment was positively correlated with overall cancer survival. is a little-reported gene in tumors, and its mechanism of action remains unclear.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
February 2022
Degradable vinyl polymers by radical ring-opening polymerization are promising solutions to the challenges caused by non-degradable vinyl plastics. However, achieving even distributions of labile functional groups in the backbone of degradable vinyl polymers remains challenging. Herein, we report a photocatalytic approach to degradable vinyl random copolymers via radical ring-opening cascade copolymerization (rROCCP).
View Article and Find Full Text PDFAngew Chem Int Ed Engl
March 2021
We report an electrochemical method for coupling biomass-derived C5/C6 compounds to value-added fuel precursors. Using only 2 % of equivalent charges, 2-methylfuran (2-MF) was oxidized to yield a cation radical, which readily reacted with 3-hexene-2,5-dione, a derivate of 2,5-dimethylfuran, to produce 3-(5-methylfuran-2-yl)hexane-2,5-dione. The product was converted to 4-ethylnonane (a component of biodiesel/jet fuel) in a single step in excellent yield.
View Article and Find Full Text PDFA novel strategy for the synthesis of main-chain polymers through radical ring-closing/ring-opening cascade polymerization is reported. Efficient radical cyclopolymerization was achieved through systematic optimization of the electronic properties of 1,6-diene structures. Fusing 1,6-diene with allylic sulfide or allylic sulfone motifs enabled a ring-closing/ring-opening cascade reaction that provides a strong driving force for the ring-opening polymerization of large macrocyclic monomers.
View Article and Find Full Text PDFWe report herein an atom-economical and sustainable approach to access amidinyl radical intermediates through the anodic cleavage of N-H bonds. The resulting nitrogen-centered radicals undergo cyclizations with (hetero)arenes, followed by rearomatization, to afford functionalized tetracyclic benzimidazoles in a highly straightforward and efficient manner. This metal- and reagent-free C-H/N-H cross-coupling reaction exhibits a broad substrate scope and proceeds with high chemoselectivity.
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