Macrocycle-based glycoclusters, on account of their promising anti-adhesive properties against bacteria,are potential therapeutic alternatives to classic antibiotics through the much less explored anti-adhesive strate...Macrocycle-based glycoclusters, on account of their promising anti-adhesive properties against bacteria,are potential therapeutic alternatives to classic antibiotics through the much less explored anti-adhesive strategy. In this study, a series of constitutionally-pure pentavalent glycoclusters was prepared by conjugating assorted azido-carbohydrates onto a penta-propargyl rim-differentiated pillar[5]arene(RD-P[5])scaffold through Cu(I)-catalyzed azide–alkyne cycloaddition “click” reactions. Their binding towards therapeutically relevant bacterial lectins, such as Lec A and Lec B from Pseudomonas aeruginosa and concanavalin A(Con A), were evaluated subsequently by isothermal titration calorimetric studies. Most of these isomerfree RD-P[5] pentavalent glycoclusters, except the fucosylated ones, display good affinities to lectins.Nonetheless, the dissociation constants observed are similar to those displayed by an analogous pentavalent glycocluster consisting of four P[5] constitutional isomers, in which the RD-P[5] component merely accounts for 7% in the mixture. Our results revealed that high constitutional purity is not essential for achieving effective multivalent interactions between P[5]-based glycoclusters and lectins, presumably as a result of the conformationally labile nature of the P[5] scaffold. This information provides valuable design principles for low-cost and facile syntheses of glycosylated P[5]s for biomedical applications.展开更多
Development of novel photosensitizers(PSs)with high biocompatibility and biological uptake is of significance for efficient photodynamic anti-tumor or anti-bacterial.This study presents a smart self-assembly strategy ...Development of novel photosensitizers(PSs)with high biocompatibility and biological uptake is of significance for efficient photodynamic anti-tumor or anti-bacterial.This study presents a smart self-assembly strategy of glyco-photosensitizers with near-infrared(NIR)emission and aggregation-induced generation reactive oxygen species(AIG-ROS)ability for cell imaging and photodynamic therapy(PDT)of both tumor cells and bacteria.Two photosensitizers,KL1 and KL2,are based on a“D-π-A”molecular architecture,featuring a tricyanofuran(TCF)acceptor and a tetraphenylethene(TPE)donor bridged by thiophene derivatives.After self-assembling with TPE-based glycoclusters(TPE-Glc_4),the resulting glyco-nanoparticles(KL1-G and KL2-G)exhibit improved water solubility and AIG-ROS capability,including singlet oxygen(~1O_(2))and superoxide radicals(·O_(2)^(-))upon light irradiation.In cellular studies,TPE-glycoclusters facilitate the cellular uptake of PSs,thereby enhancing the NIR fluorescence signal and PDT efficiency for multiple kinds of cells.KL2-G shows superior phototoxicity,reducing cell viability to less than 5%at a low concentration of<5μM under light irradiation.Additionally,KL2-G exhibits potential for photodynamic anti-bacterial applications against Escherichia coli.This work underscores the importance of glycoclustersmediated delivery in therapeutic efficacy enhancement of PSs and highlights the potential of glyco-nanoparticles in bioimaging and phototherapy applications.展开更多
Correction to:Sci China Chem,2025,68(10):5086-5096.https://doi.org/10.1007/s11426-025-2730-2 We regret that our article“Smart formation of multifunctional glyco-nanoparticles:glycoclusters delivering NIR photosensiti...Correction to:Sci China Chem,2025,68(10):5086-5096.https://doi.org/10.1007/s11426-025-2730-2 We regret that our article“Smart formation of multifunctional glyco-nanoparticles:glycoclusters delivering NIR photosensitizers for enhanced cell imaging and photodynamic therapy”(Sci China Chem,2025,68:5086-5096)contained errors.Specifically,the image in Figure 6d exhibiting the phototoxicity of control group at 0μM was inadvertently taken the incorrect image in the original paper.The correction version is given below.Nevertheless,this correction does not affect the results and conclusion of the paper.展开更多
The Ugi four-component reaction (U-4CR) was utilized to prepare divalent and trivalent cluster mannosides. Thus, two target compounds 6 and 8 were obtained efficiently using carboxymethyl 2, 3, 4, 6-tetra-O-acetyl--D-...The Ugi four-component reaction (U-4CR) was utilized to prepare divalent and trivalent cluster mannosides. Thus, two target compounds 6 and 8 were obtained efficiently using carboxymethyl 2, 3, 4, 6-tetra-O-acetyl--D-mannopyranoside 4 as acid component, and 1, 6-hexanediamine or tris(2-aminoethyl)amine as the multivalent scaffolds.展开更多
A novel triazatruxene-based fluorescent glycocluster was synthesized and its selective binding interactions with PNA lectin were investigated by fluorescence spectroscopy,CD spectroscopy,and a turbidity assay.The glyc...A novel triazatruxene-based fluorescent glycocluster was synthesized and its selective binding interactions with PNA lectin were investigated by fluorescence spectroscopy,CD spectroscopy,and a turbidity assay.The glycocluster exhibited a strong binding affinity for PNA lectin with a Stern-Volmer quenching constant of 5.8×10^5 mol^-1L展开更多
The specific trigger of tumor cell ferroptosis is an effective way for precise cancer therapy with low side effects and high efficiency.However,the trigger reagents should be further developed.Herein,an ATT((E)-2,2...The specific trigger of tumor cell ferroptosis is an effective way for precise cancer therapy with low side effects and high efficiency.However,the trigger reagents should be further developed.Herein,an ATT((E)-2,2'-(((1,2-diphenylethene-1,2-diyl)bis(4,1-phenylene))bis(2-(4-(dicyanomethylene)-2,3,5,6-tetrafluorocyclohexa-2,5-dien-1-ylidene)-2-(4-(diphenylamino)phenyl)ethan-1-yl-1-ylidene))dimalononitrile)reagent bearing cyano and perfluorophenyl groups was found to be a capable reaction with cysteine(Cys)based on a single electron transfer(SET)mechanism in a concentration-dependent manner.Remarkably,with the depletion of Cys,the synthesis of glutathione(GSH)is inhibited intracellularly,which leads to ferroptosis and enhances the sensitivity of tumor cells towards paclitaxel,resulting in efficient inhibition of tumor cells.Meanwhile,the fluorescence of the system is enhanced significantly by destroying the intramolecular charge transfer process of ATT after its reaction with Cys,realizing the self-indication of the treatment.Based on this synergistic treatment,the efficient and specific suppression of tumor cells both in vitro and in vivo is realized,providing a reliable and promising strategy for cancer treatment in the clinic.展开更多
Structurally well defined di-, tri- and tetra-valent cluster galactosides were synthesized in a convenient way. Oligo-glutamic acids were assembled as scaffolds. The presence of amine groups in these three ligands is ...Structurally well defined di-, tri- and tetra-valent cluster galactosides were synthesized in a convenient way. Oligo-glutamic acids were assembled as scaffolds. The presence of amine groups in these three ligands is expected to couple with drugs or genes for delivery. The binding affinities of these cluster galactoses to liver cells were de-termined by in vitro binding studies. Among them, the tetravalent cluster galactose (19) showed the highest affinity to liver cell. It is therefore a promising targeting device for the specific delivery of drugs or genes to parenchymal liver cells.展开更多
基金Financial supports from the National Natural Science Foundation of China (No. 21801184)the Tianjin Municipal Applied Basic and Key Research Scheme of China (No. 18JCQNJC06400)+3 种基金Xiamen University, Starry Night Science Fund of Zhejiang University Shanghai Institute for Advanced Study (No. SN-ZJU-SIAS-006)Université de Lyon, the French Agence Nationale de la Recherche (Dyna Sweet, ANR-08-BLAN-0305)Glyco@Alps (ANR-15-IDEX-02)Labex Arcane/CBH-EUR-GS (ANR-17-EURE-0003) are gratefully acknowledged。
文摘Macrocycle-based glycoclusters, on account of their promising anti-adhesive properties against bacteria,are potential therapeutic alternatives to classic antibiotics through the much less explored anti-adhesive strategy. In this study, a series of constitutionally-pure pentavalent glycoclusters was prepared by conjugating assorted azido-carbohydrates onto a penta-propargyl rim-differentiated pillar[5]arene(RD-P[5])scaffold through Cu(I)-catalyzed azide–alkyne cycloaddition “click” reactions. Their binding towards therapeutically relevant bacterial lectins, such as Lec A and Lec B from Pseudomonas aeruginosa and concanavalin A(Con A), were evaluated subsequently by isothermal titration calorimetric studies. Most of these isomerfree RD-P[5] pentavalent glycoclusters, except the fucosylated ones, display good affinities to lectins.Nonetheless, the dissociation constants observed are similar to those displayed by an analogous pentavalent glycocluster consisting of four P[5] constitutional isomers, in which the RD-P[5] component merely accounts for 7% in the mixture. Our results revealed that high constitutional purity is not essential for achieving effective multivalent interactions between P[5]-based glycoclusters and lectins, presumably as a result of the conformationally labile nature of the P[5] scaffold. This information provides valuable design principles for low-cost and facile syntheses of glycosylated P[5]s for biomedical applications.
基金supported by the National Natural Science Foundation of China(22305178,22207086,22107029,22377135)the Shandong Provincial Natural Science Foundation(ZR2023QB248,ZR2022QH060)+5 种基金the Taishan Scholars Program(tsqn202312305)the Young Elite Scientists Sponsorship Program by Chinese Chemical Societythe Fundamental Research Projects of Science&Technology Innovation and Development Plan in Yantai City(2023JCYJ059)the Key R&D Program of Shandong Province,China(2024CXPT028)the Science and Technology Support Plan for Youth Innovation in Universities of Shandong Province(2024KJG029)the Shandong Laboratory Program(SYS202205)。
文摘Development of novel photosensitizers(PSs)with high biocompatibility and biological uptake is of significance for efficient photodynamic anti-tumor or anti-bacterial.This study presents a smart self-assembly strategy of glyco-photosensitizers with near-infrared(NIR)emission and aggregation-induced generation reactive oxygen species(AIG-ROS)ability for cell imaging and photodynamic therapy(PDT)of both tumor cells and bacteria.Two photosensitizers,KL1 and KL2,are based on a“D-π-A”molecular architecture,featuring a tricyanofuran(TCF)acceptor and a tetraphenylethene(TPE)donor bridged by thiophene derivatives.After self-assembling with TPE-based glycoclusters(TPE-Glc_4),the resulting glyco-nanoparticles(KL1-G and KL2-G)exhibit improved water solubility and AIG-ROS capability,including singlet oxygen(~1O_(2))and superoxide radicals(·O_(2)^(-))upon light irradiation.In cellular studies,TPE-glycoclusters facilitate the cellular uptake of PSs,thereby enhancing the NIR fluorescence signal and PDT efficiency for multiple kinds of cells.KL2-G shows superior phototoxicity,reducing cell viability to less than 5%at a low concentration of<5μM under light irradiation.Additionally,KL2-G exhibits potential for photodynamic anti-bacterial applications against Escherichia coli.This work underscores the importance of glycoclustersmediated delivery in therapeutic efficacy enhancement of PSs and highlights the potential of glyco-nanoparticles in bioimaging and phototherapy applications.
文摘Correction to:Sci China Chem,2025,68(10):5086-5096.https://doi.org/10.1007/s11426-025-2730-2 We regret that our article“Smart formation of multifunctional glyco-nanoparticles:glycoclusters delivering NIR photosensitizers for enhanced cell imaging and photodynamic therapy”(Sci China Chem,2025,68:5086-5096)contained errors.Specifically,the image in Figure 6d exhibiting the phototoxicity of control group at 0μM was inadvertently taken the incorrect image in the original paper.The correction version is given below.Nevertheless,this correction does not affect the results and conclusion of the paper.
文摘The Ugi four-component reaction (U-4CR) was utilized to prepare divalent and trivalent cluster mannosides. Thus, two target compounds 6 and 8 were obtained efficiently using carboxymethyl 2, 3, 4, 6-tetra-O-acetyl--D-mannopyranoside 4 as acid component, and 1, 6-hexanediamine or tris(2-aminoethyl)amine as the multivalent scaffolds.
基金supported by the National Natural Science Foundation of China(Nos.21002020 and 21172051)the Hebei Natural Science Foundation(Nos.B2011201052 and B2012201041)
文摘A novel triazatruxene-based fluorescent glycocluster was synthesized and its selective binding interactions with PNA lectin were investigated by fluorescence spectroscopy,CD spectroscopy,and a turbidity assay.The glycocluster exhibited a strong binding affinity for PNA lectin with a Stern-Volmer quenching constant of 5.8×10^5 mol^-1L
基金supported by the Key-Area Research and Development Program of Guangdong Province(2024B0101040001)the National Natural Science Foundation of China(21788102,21907034)+1 种基金the Fund of Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates(2023B1212060003)the Innovation and Technology Commission of Hong Kong(ITC-CNERC14SC01).
文摘The specific trigger of tumor cell ferroptosis is an effective way for precise cancer therapy with low side effects and high efficiency.However,the trigger reagents should be further developed.Herein,an ATT((E)-2,2'-(((1,2-diphenylethene-1,2-diyl)bis(4,1-phenylene))bis(2-(4-(dicyanomethylene)-2,3,5,6-tetrafluorocyclohexa-2,5-dien-1-ylidene)-2-(4-(diphenylamino)phenyl)ethan-1-yl-1-ylidene))dimalononitrile)reagent bearing cyano and perfluorophenyl groups was found to be a capable reaction with cysteine(Cys)based on a single electron transfer(SET)mechanism in a concentration-dependent manner.Remarkably,with the depletion of Cys,the synthesis of glutathione(GSH)is inhibited intracellularly,which leads to ferroptosis and enhances the sensitivity of tumor cells towards paclitaxel,resulting in efficient inhibition of tumor cells.Meanwhile,the fluorescence of the system is enhanced significantly by destroying the intramolecular charge transfer process of ATT after its reaction with Cys,realizing the self-indication of the treatment.Based on this synergistic treatment,the efficient and specific suppression of tumor cells both in vitro and in vivo is realized,providing a reliable and promising strategy for cancer treatment in the clinic.
基金Project supported by the Ministry of Science and Technology of China (No. 2001CCA01600).
文摘Structurally well defined di-, tri- and tetra-valent cluster galactosides were synthesized in a convenient way. Oligo-glutamic acids were assembled as scaffolds. The presence of amine groups in these three ligands is expected to couple with drugs or genes for delivery. The binding affinities of these cluster galactoses to liver cells were de-termined by in vitro binding studies. Among them, the tetravalent cluster galactose (19) showed the highest affinity to liver cell. It is therefore a promising targeting device for the specific delivery of drugs or genes to parenchymal liver cells.
