Wavelength-Controlled Light-Responsive Polymer Vesicle Based on Se–S Dynamic Chemistry

Peng Zhao, Jiahao Xia, Muqing Cao, Huaping Xu ACS Macro Lett., 2020, 9, 163-168. Wavelength-controlled Se–S dynamic chemistry was put forward recently as a convenient way to regulate the balance of a selenide sulfide exchange reaction. In this paper, we synthesized an asymmetric polymeric amphiphile linked with a Se–S bond and then induced it to self-assemble into vesicles in water. When the visible light was applied to the assembly solution with addition of toluene, Se–S bonds containing vesicles were ruptured. Thus, the wavelength-controlled light responses of relatively stable polymer a...
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Diselenide-Pemetrexed Assemblies for Combined Cancer Immuno-, Radio-, and Chemotherapies

Tianyu Li, Shuojiong Pan, Shiqian Gao, Wentian Xiang, Chenxing Sun, Wei Cao, Huaping Xu Angew. Chem. Int. Ed., 2020, 59, 2700-2704. Immunotherapy has emerged as a promising new approach for cancer treatment. However, clinically available drugs have been limited until recently, and the antitumor efficacy of most cancer immunotherapies still needs to be improved. Herein, we develop diselenide-pemetrexed assemblies that combine nature killer (NK) cell-based cancer immunotherapy with radiotherapy and chemotherapy in a single system. The assemblies are prepared via co-assembly between pemetre...
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Measuring the Strength of S/Se Based Dynamic Covalent Bonds

Jiahao Xia, Hongbin Li, Huaping Xu Acta Polym. Sin., 2020, 51, 205. Sulfur, selenium-containing bonds, including disufide bond (SS), diselenide bond (SeSe) and selenide-sulfide bond (SeS), are an important type of light responsive dynamic covalent bonds. Among them SS and SeS bond can undergo exchange reaction with the irridiation of UV light while SeSe bond only requires visible light. In this paper we prepared SS or SeSe bond modified quartz substrate via surface modification. Based on the light induced exchange reaction we can obtain polymer chain attached substrates linked by a singl...
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Selenoxide Elimination Manipulate the Oxidative Stress to Improve the Antitumor Efficacy

Chenxing Sun, Lu Wang, Banruo Xianyu, Tianyu Li, Shiqian Gao, Huaping Xu Biomaterials, 2019, 225, 119514. Selenoxide elimination reaction has been widely used in the field of organic synthesis. However, few studies have been conducted to apply this reaction in biodegradable nanomedicine. In this work, the selenoxide elimination reaction was used for cancer treatment via producing excess cellular reactive oxygen species (ROS) for the first time. The β-seleno diesters and porphyrin derivates containing nanoparticle could be responsive to the intracellular ROS and produce acrylates through ...
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Selenium-Containing Supra-Amphiphiles

Wei Cao, Huaping Xu Mater. Chem. Front., 2019, 3, 2010-2017. Supra-amphiphiles formed by noncovalent interactions are a versatile bottom-up fabrication strategy for functional soft materials. Selenium chemistry possesses many unique properties and selenium-containing polymers made by covalent synthesis have developed enormously in the past few decades. Supra-amphiphiles built on selenium-containing species offer more opportunities for functional systems without too many synthetic efforts. This review will give a brief overview of different types of selenium-containing supra-amphiphiles b...
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Diselenide-Containing Polymeric Vesicles with Osmotic Pressure Response

Jiahao Xia, Peng Zhao, Shuojiong Pan, and Huaping Xu ACS Macro Lett., 2019, 8, 629−633 Mechanophore is a kind of functional group that can undergo chemical reactions when given mechanical force stimuli. In this paper, osmotic pressure was used as an external force to trigger a diselenide exchange reaction. A diselenide bond containing block polymer capable of self-assembling to a vesicle structure and an ester bond containing a counterpart were synthesized in this study. When NaCl was added into the solution to generate the osmotic pressure difffference inside and outside vesicles, disel...
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ROS-triggered Degradation of Selenide-containing Polymers Based on Selenoxide Elimination

Lu Wang, Kuixin Zhu, Wei Cao, Chenxing Sun, Chenjie Lu and Huaping Xu Polym. Chem., 2019, 10, 2039 – 2046. Synthetic degradable polymers for biomedical applications have drawn considerable attention because of the nonnegligible environmental pollution and bioaccumulation caused by nondegradable synthetic polymers. We developed a new degradable reactive oxygen species (ROS) responsive selenide-containing polymer that can depolymerize controllably through selenoxide elimination reactions. β-selenylated carbonyl groups were employed in the main chains for oxidation induced degradation inste...
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Quantifying the Bonding Strength of Gold-Chalcogen Bonds in Block Copolymer Systems

Wentian Xiang, Zhandong Li, Cong-Qiao Xu, Jun Li, Wenke Zhang, and Huaping Xu Chem. Asian J. 2019, 14, 1481–1486. Gold–chalcogen interactions are ubiquitous in gold biological and medicinal systems. Understanding the nature of these interactions can provide the basis for regulating their structures and functionalities and a reasonable way to interpret the differences in various properties. However, the relative strength of gold–chalcogen bonds remains controversial, and the conclusions of many related works are inconsistent. Thus, in this work, we successfully quantified the relative strengt...
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Surface Modification Based on Diselenide Dynamic Chemistry:Towards Liquid Motion and Surface Bioconjugation

Jiahao Xia, Peng Zhao, Ke Zheng, Chenjie Lu, Shouchun Yin and Huaping Xu Angew. Chem. Int. Ed., 2019, 131, 552-556. Surface modification is an important technique in fields, such as, self‐cleaning, surface patterning, sensing, and detection. The diselenide bond was shown to be a dynamic covalent bond that can undergo a diselenide metathesis reaction simply under visible light irradiation. Herein we develop this diselenide dynamic chemistry into a versatile surface modification method with a fast response and reversibility. The diselenide bond could be modified onto various substrates, su...
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Wavelength-Controlled Dynamic Metathesis: A Light-Driven Exchange Reaction Between Disulfide and Diselenide Bonds

Fuqiang Fan, Shaobo Ji, Chenxing Sun, Cheng Liu, Ying Yu, Yu Fu and Huaping Xu Angew. Chem. Int. Ed., 2018, 57, 16426-16430. Though wavelength-controlled dynamic processes have been well developed, they mostly consist of light-triggered isomerization or the cleavage/formation of molecular connections. Control over dynamic metathesis reactions by different light wavelengths, which would be useful in controllable dynamic chemistry, has rarely been studied. Herein, taking advantage of the different bond energies of disulfide bonds and diselenide bonds, we realized a wavelength-driven exchange r...
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