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REACTIVE & FUNCTIONAL POLYMERS · 2011 · IF 2.546

Synthesis and properties of polyamides containing high contents of thioether units

Gang Zhang,Dong-sheng Li,Guang-shun Huang,Xiao-jun Wang,Sheng-ru Long,Jie Yang

Two kinds of monomers containing the thioether units 4,4′-thiodibenzoyl chloride (T-DC) and 4,4′-bis(4-chloroformylphenylthio)benzene (BPB-DC) were synthesized in two steps and were reacted with diamine-containing thioether (–S–) and sulfone units to prepare a polyamide containing high contents of thioether groups. The intrinsic viscosities of the polyamides were 0.81–0.93   dl/g. These polymers had good optical properties , including an optical transmittance of the aromatic polyamide film at 450   nm that was higher than 90%. Additionally, the high quantity of thioether units provided the polymers with high refractive indices of 1.710–1.716 and low birefringences of 0.007–0.009. These polyamides also had excellent thermal properties, with glass transition temperatures ( T g ) of 230–246   °C and initial degradation temperatures ( T d ) of 477–473   °C. Finally, they showed improved solubility in polar aprotic solvents .

研究领域: 材料科学 · 化学工程
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POLYMER INTERNATIONAL · 2012 ·Vol. 61 ·期 5 ·800-809 · IF 1.902

Effects of thioether content on thermal and optical properties of polyamides

Gang Zhang,Jiangjun Hu,Huiwen Yang,Xiaojun Wang,Shengru Long,Jie Yang

4,4′-Bis(4-chloroformylphenylthio)benzene was synthesized in two steps and was reacted with diamine-containing thioether and amide units to prepare a polyamide containing high contents of thioether groups. The intrinsic viscosities of the polyamides were 0.76–0.87 dL g −1 . These polyamides had excellent thermal properties, with glass transition temperatures of 234.8–269 °C and initial degradation temperatures of 461–469.7 °C. They showed improved solubility in polar aprotic solvents and could form moderate strength films with a tensile strength of 75.2–111.6 MPa and storage modulus of 1.0–1.3 GPa (at 220 °C). These polymer films also had good optical properties, including an optical transmittance of the aromatic polyamide film at 450 nm that was higher than 90%. Additionally, the high quantity of thioether units provided the polymers with high refractive indices of 1.700–1.704 and low birefringences of 0.007–0.008. Copyright © 2012 Society of Chemical Industry

研究领域: 材料科学 · 高分子化学
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BIOMACROMOLECULES · 2019 · IF 5.667

Synthesis of an Oxidation-Sensitive Polyphosphoester Bearing Thioether Group for Triggered Drug Release

Jihong Wang,Dongdong Li,Wei Tao,Yang Lu,Xianzhu Yang,Jun Wang

In this work, novel amphiphilic diblock copolymers of polyethylene glycol and polyphosphoester with pendant thioether groups, denoted as mPEG-b-PMSPEP, were synthesized through the ring-opening polymerization of functionalized cyclic phosphoester monomer using methoxy poly(ethylene glycol) and Sn(Oct)2 as the macroinitiator and catalyst, respectively. The successful synthesis was confirmed by 1H, 13C, 31P nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC). These amphiphilic block copolymers self-assembled spontaneously in the aqueous solution, and the formed nanoparticles were sensitive to the oxidation that induced the hydrophobic to hydrophilic transition for its PMSPEP core under triggering of H2O2 and the subsequent dissociation of the nanoparticles. In addition, the reactive oxygen species (ROS) generated by light and the photosensitizer were also capable of carrying out the oxidation of these nanoparticles. Their oxidation profiles were systemically evaluated by 1H NMR. Finally, the mPEG-b-PMSPEP nanoparticles were used to coencapsulate the photosensitizer chlorin e6 (Ce6) and anticancer drug paclitaxel (PTX), achieving the photoaccelerated PTX release via oxidation of the nanoparticles by the generated ROS under light irradiation. Meanwhile, the in vitro cytotoxicity assays indicated that these nanoparticles coencapsulated with PTX and Ce6 showed a combined cell-killing effect toward MDA-MB-231 tumor cells, exhibiting great potential for drug delivery systems that realize the synergistic chemo-photodynamic therapy for cancer treatment.

CAS / MDL: 505-10-2
研究领域: 生物材料 · 药剂学 · 肿瘤治疗
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2019 · IF 2.931

The functionalized ruthenium(II) polypyridine complexes for the highly selective sensing of mercury ions

Jiru Xu,Yonghua Liu,Mei-Jin Li

A series of new ruthenium(II) polypyridine complexes appending with thioether groups were designed, synthesized and characterized. The sensing ability of the complexes toward mercury ions were studied by electronic absorption and emission spectra, and the reaction of the complexes with mercury ions were also confirmed by ESI mass spectroscopy and 1 HNMR spectroscopy. The thioether groups would react with mercury ion fast to form aldehyde group leading to the significant change in the spectra. The color of the complex changed from yellow to orange after addition of mercury ions, and the color of the emission changed from red orange to dark red with a large red shift (~80 nm). Importantly, these kinds of ruthenium(II) complexes show a unique recognition of mercury ions over other metal ions . The complexes with more thioether groups also showed a better sensitivity toward mercury ions, this is good strategy for the further design of the new phosphorescent probes for sensing of mercury ions.

CAS / MDL: 3109-63-5
研究领域: 分析化学 · 环境科学 · 材料科学
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POLYMER · 2021 · IF 4.43

Design of recyclable, fast-responsive and high temperature shape memory semi-aromatic polyamide

Guang-ming Yan,Han Wang,Dong-sheng Li,Hao-ran Lu,Sui-lin Liu,Jie Yang,Gang Zhang

Development of high temperature shape memory polymers with fast response time and recyclable performance is highly desired. In this study, a new semi-aromatic tri-amine (TRIA) containing thioether unit is prepared through the reaction of trifluoro-monomer and p-mercaptoaniline (p-MA). It is conducted to polymerize with 4,4′-thiodibenzoyl chloride (TDC) and different ratios of diamine (both of them contained flexible thioether group) to supply a series of slightly crosslinking semi-aromatic polyamide . It is found that the resultant polymers had excellent thermal properties (T g , 237.9–245.8 °C, T d , 430.9–436.5 °C) and mechanical properties (tensile strength, 74–100 MPa). Because of the introduction of the large amount of flexible thioether group, the resultant polyamides can be dissolved in some aprotic solvents , and can be processed with solution method to fabricate a series of fast-responsive shape memory film (SMF) with a responsive time of 6–8 s, recovery rate of 98–99.5% after 20 cycles. What's more, the oxidized film can even lift a weight equal to about 2–3 times (vertical direction) and 5–8 times (horizontal direction) of its own weight. Interestingly, unlike other shape memory polymers, these SMF after multiple processes (after bending-recovery cycle at high temperature) can still be processed repeatedly with a solution route, which supplies a novel and recyclable candidate for excellent performance SMP. It is expected to be used in solar cell wingspan actuator to light the satellite weight.

CAS / MDL: 111-40-0
研究领域: 材料科学 · 高分子化学
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MACROMOLECULAR BIOSCIENCE · 2023 ·Vol. 23 ·期 3 ·2200498 · IF 4.6

Oxidation Responsive PEGylated Polyamino Acid Bearing Thioether Pendants for Enhanced Anticancer Drug Delivery

Yitao Sun,Yu Zhang,Xin Guo,Yanping Wang,Pan He,Chunsheng Xiao

Reactive oxygen species (ROS) in biological tissues are in a state of dynamic balance. However, many diseases such as cancer and inflammation, are accompanied by a long-term increase in ROS. This situation inspires researchers to use ROS-sensitive nanocarriers for a site-specific release of cargo in pathological areas. Polyamino acid materials with good biodegradability, biocompatibility, and regular secondary structure are widely used in the biomedical field. Herein, a new oxidation responsive PEGylated polyamino acid is synthesised for anticancer drug delivery by ring-opening polymerisation of N -carboxyanhydrides bearing thioether pendants. The obtained block copolymer mPEG- b -PMLG self-assembles into spherical nanoparticles (NPs) in water with diameter ≈68.3 nm. NMR measurement demonstrated that the hydrophobic thioether pendants in the NPs can be selectively oxidised to hydrophilic sulfoxide groups by H 2 O 2 , which will lead to the disassociation of NPs. In vitro drug release results indicated that the encapsulated Nile red is selectively released in the trigger of 10 mM H 2 O 2 in PBS. Finally, anticancer drug doxorubicin (DOX) is encapsulated to the NPs, and the obtained NPs/DOX exhibits an improved antitumor efficacy in 4T1 tumour-bearing mice and lower cardiotoxicity than free DOX. These results indicates that the mPEG- b -PMLG NPs are promising for anticancer drug delivery.

CAS / MDL: 24277-39-2
研究领域: 生物材料学 · 药剂学 · 肿瘤学
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Journal of Materials Chemistry A · 2018 ·Vol. 6 ·期 26 ·12323-12333 · IF 9.931

Controllable synthesis of hollow periodic mesoporous organosilica spheres with radial mesochannels and their degradable behavior

Yangyi Sun,Min Chen,Limin Wu

Hollow periodic mesoporous organosilica spheres (HPMOSs) have some important special applications owing to their unique properties, but current syntheses usually involve various template methods that are time-consuming. Herein, we report a highly efficient and controllable synthesis of HPMOSs with radial mesochannels, only through introducing a pre-hydrolysis process to the commercially available bissilylated organosilanes (R′O)3Si–R–Si(OR′)3 with CTAB. The HPMOSs are robust with a mean diameter as small as 45 nm and a shell thickness as thin as 14 nm. A cytotoxicity assay indicates that the obtained HPMOSs possess good biocompatibility, and the HPMOSs with thioether groups are degradable under a 10 mM glutathione microenvironment. The amphiphilic organosilica precursors derived from the pre-hydrolysis process, CTAB micelles, and ethanol contribute to the formation of the HPMOSs.

研究领域: 材料科学 · 纳米技术 · 化学工程 · 生物医学工程
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JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY · 2025 · IF 6.2

Discovery of Novel Pyrazole-4-carboxamide Derivatives with Thioether Moiety as Potential SDHI Agents for Crop Protection

Bo Luo,Yanbing Wu,Mengfan Cao,Chendan Liu,Heran Xiong,Yuqing Guo,Miao Wang,Lu Yu,Ruxin Han,Mengxing Liu

In the ongoing search for more potent succinate dehydrogenase inhibitors (SDHIs) for agricultural applications, 30 pyrazole-4-carboxamide derivatives bearing a thioether group were designed and synthesized via bioisosteric replacement and scaffold-hopping based on the structure of two SDHIs lead compounds in our previous work. The antifungal efficacy of these target compounds was evaluated against five major plant pathogenic fungi, and the results indicated that the majority of the synthesized compounds exhibited strong antifungal activities, particularly against Rhizoctonia solani and Sclerotinia sclerotiorum. Among these, compound 8e emerged as the most promising candidate, displaying exceptional antifungal potency against R. solani (EC50 = 0.012 μg/mL) and S. sclerotiorum (EC50 = 0.123 μg/mL), significantly superior to boscalid (EC50 = 0.464 μg/mL and 0.159 μg/mL, respectively) and comparable to fluxapyroxad (EC50 = 0.036 μg/mL and 0.104 μg/mL). Additionally, detached leaf assays revealed that compound 8e effectively inhibited the growth of R. solani on rice leaves and S. sclerotiorum on oilseed rape leaves, achieving significant protective efficacies of 89.1% and 93.9%, respectively, at 100 μg/mL, which were superior to boscalid (68.8% and 90.5%) and comparable to fluxapyroxad (86.4% and 98.6%), indicating a promising potential for crop protection in the field, particularly for rice and oilseed rape. Furthermore, SDH enzymatic inhibition assays showed that compound 8e exhibited potent SDH inhibition (IC50 = 1.30 μM), which was more effective than boscalid (IC50 = 1.53 μM) and close to fluxapyroxad (IC50 = 0.35 μM), confirming its role as an effective SDHI. SEM analysis showed that compound 8e caused significant structural disruption and morphological damage to the hyphae of R. solani, further supporting its antifungal activity. The results of molecular docking and DFT and ESP calculations demonstrated that compound 8e had a similar antifungal mechanism to fluxapyroxad. These findings suggested that compound 8e held great promise as a potential SDHI candidate for protection of crops such as rice and oilseed rape, warranting further investigation.

研究领域: 农业化学 · 药物化学 · 植物病理学 · 生物化学 · 农药科学 · 计算生物学
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CELLULOSE · 2019 ·Vol. 26 ·期 17 ·9323-9333 · IF 3.917

A hybrid binder of carboxymethyl chitosan and l-methionine enables a slight amount of Ag NPs to be durably effective on antibacterial cotton fabrics

Zhou Jing,Hu XinYue,Zhu YiYuan,Lyu HongFen,Zhang Lei,Fu FeiYa,Liu XiangDong

This work proposes a facile approach to improve the durability of antibacterial cotton fabric by using carboxymethyl chitosan (CMC) and l -methionine (Met) as a combination binder to immobilize silver nanoparticles (Ag NPs). The durable antibacterial function is achieved by grafting CMC and Met molecules onto a cotton fabric by a simple pad-dry-cure process, followed by the preparation of Ag NPs on the modified surface. This surface modification process provides the cotton fabric with an excellent antibacterial effect and outstanding laundering durability. Structural analyses of the modified surface revealed that the covalent bonds between Met, CMC, and cotton fibers were formed, and the thioether groups caused the stable immobilization of the Ag NPs. Notably, the modification process does not significantly damage the original fiber structure. The desired cotton properties such as vapor permeability, water absorptivity, and flexibility of the modified fabric were very close to the original cotton. Moreover, the safety to human skin was verified by cytotoxicity tests using fibroblast cells.

研究领域: 材料科学 · 纺织工程 · 纳米技术 · 生物医学工程
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