A novel geminal imidazolium ionic liquid with long hydrocarbon group, 1,4-bis （3-tetradecylimidazolium- 1-yl） butane bromide was synthesized and an efficient synthesized method was introduced detailedly. Its structu...A novel geminal imidazolium ionic liquid with long hydrocarbon group, 1,4-bis （3-tetradecylimidazolium- 1-yl） butane bromide was synthesized and an efficient synthesized method was introduced detailedly. Its structure was determined by FT-IR, ^1H NMR and elemental analysis.展开更多
Spin-crossover(SCO)molecules have been proposed for applications in molecular spintronic devices due to their bistability which can be reversibly switched by an external stimulus.Here,we report the synthesis,structure...Spin-crossover(SCO)molecules have been proposed for applications in molecular spintronic devices due to their bistability which can be reversibly switched by an external stimulus.Here,we report the synthesis,structure and characterization of an Fe(Ⅱ)complex,FeL_(2)(L=N’-(pyridin-2-ylmethylene)-4-(undec-10-en-1-yloxy)benzohydrazide),having long aliphatic chains with terminal C=C bonds.Variable-temperature Single Crystal X-ray Diffraction(SCXRD)and magnetic susceptibility measurements reveal that the SCO behavior with a thermal hysteresis loop originates from the combination of the change of the Fe(Ⅱ)center coordination environment and the thermal motion of long aliphatic chains.Differential Scanning Calorimetry(DSC),variable-temperature Powder X-ray Diffraction(PXRD)and Polarized Optical Microscopy(POM)measurements suggest that the latter is also associated with a crystal–liquid crystal(LC)phase transition at high temperatures.Together,these results provide the prerequisites for potential applications of bistable SCO molecules in spintronic devices and liquid crystal displays.展开更多
In the domain of high-performance engineering polymers, the enhancement of mechanical flexibility in poly(phenylene sulfide) (PPS) resins has long posed a significant challenge. A novel molecular structure, designated...In the domain of high-performance engineering polymers, the enhancement of mechanical flexibility in poly(phenylene sulfide) (PPS) resins has long posed a significant challenge. A novel molecular structure, designated as PP-He-IS, wherein imide rings and an aliphatic hexylene chain are covalently incorporated into the PPS backbone to enhance its flexibility, is introduced in this study. Molecular dynamics (MD) simulations are employed to systematically explore the effects of diversifying the backbone chain structures by substituting phenyl units with alkyl chains of varying lengths, referred to as PP-A-IS where “A” signifies the distinct intermediary alkyl chain configurations. Computational analyses reveal a discernable decrement in the glass transition temperature (Tg) and elastic modulus, counterbalanced by an increment in yield strength as the alkyl chain length is extended. Notably, the PP-He-IS variant is shown to exhibit superior yield strength while simultaneously maintaining reduced elastic modulus and Tg values, positioning it as an advantageous candidate for flexible PPS applications. Mesoscopic analyses further indicate that structures such as PP-He-IS, PP-Pe-IS, and PP-Bu-IS manifest remarkable flexibility, attributable to the presence of freely rotatable carbon-carbon single bonds. Experimental validation confirms that a melting temperature of 504 K which is lower than that of conventional PPS, and lower crystallinity are exhibited by PP-He-IS, thereby affording enhanced processability without compromising inherent thermal stability. Novel insights into the strategic modification of PPS for mechanical flexibility are thus furnished by this study, which also accentuates the pivotal role played by molecular dynamics simulations in spearheading high-throughput investigations in polymer material modifications.展开更多
Two novel hexacoordinated Co(II)-based single-ion magnets were prepared and characterised.Both neutral complexes feature metal-centred coordination with one terminal and one bidentate nitrate anions along with trident...Two novel hexacoordinated Co(II)-based single-ion magnets were prepared and characterised.Both neutral complexes feature metal-centred coordination with one terminal and one bidentate nitrate anions along with tridentate derivatives of a 2,6-bis(1H-benzimidazole-2-yl)pyridine ligand containing either n-octyl(complex 1)or n-dodecyl(complex 2)chains.The presence of long aliphatic chains ensures their solubility in low polarity and volatile solvents frequently used for lithography patterning.This enabled the preparation of microstructural layers and patterns on technologically relevant substrates by easy-tohandle and low-cost wet lithographic techniques.On the other hand,attempts at surface deposition via sublimation were not successful due to thermal instability.展开更多
The clinical utility of irinotecan is restricted by individual variability in carboxylesterase expression.Direct administration of its active metabolite,7-ethyl-10-hydroxycamptothecin(SN38),presents an appealing alter...The clinical utility of irinotecan is restricted by individual variability in carboxylesterase expression.Direct administration of its active metabolite,7-ethyl-10-hydroxycamptothecin(SN38),presents an appealing alternative due to its potent anti-tumor efficacy.However,the undesirable properties of SN38,such as poor water solubility and nontarget toxicity,present significant hurdles to its clinical development.Prodrug nanoassemblies based on modular design strategy show promise in overcoming these challenges by enhancing drug delivery and selective activation.In modular design,the modification module plays a crucial role in improving the self-assembly capability of prodrugs.While current studies mainly focus on using straight aliphatic chains for prodrug design,branched aliphatic chains emerge as superior alternatives warranting further investigation.In this study,we selected 2-heptylundecanol(BAlc18)as modification module to construct an SN38 prodrug.Through exquisite design,SN38-SS-BAlc18 NPs integrated prominent properties in selfassembly capability,specific activation and biocompatibility,resolving the challenges of irinotecan and SN38,ultimately demonstrating excellent anti-tumor efficacy.This exploration enriched the design theory of prodrug nanoassemblies that can effectively balance safety and colorectal anti-tumor efficacy.展开更多
文摘A novel geminal imidazolium ionic liquid with long hydrocarbon group, 1,4-bis （3-tetradecylimidazolium- 1-yl） butane bromide was synthesized and an efficient synthesized method was introduced detailedly. Its structure was determined by FT-IR, ^1H NMR and elemental analysis.
基金the National Natural Science Foundation of China(Grant 21871247)the Key Research Program of Frontier Sciences,CAS(Grant ZDBS-LY-SLH023)for financial supportthe support of the Royal Society-Newton Advanced Fellowship(NA160075).
文摘Spin-crossover(SCO)molecules have been proposed for applications in molecular spintronic devices due to their bistability which can be reversibly switched by an external stimulus.Here,we report the synthesis,structure and characterization of an Fe(Ⅱ)complex,FeL_(2)(L=N’-(pyridin-2-ylmethylene)-4-(undec-10-en-1-yloxy)benzohydrazide),having long aliphatic chains with terminal C=C bonds.Variable-temperature Single Crystal X-ray Diffraction(SCXRD)and magnetic susceptibility measurements reveal that the SCO behavior with a thermal hysteresis loop originates from the combination of the change of the Fe(Ⅱ)center coordination environment and the thermal motion of long aliphatic chains.Differential Scanning Calorimetry(DSC),variable-temperature Powder X-ray Diffraction(PXRD)and Polarized Optical Microscopy(POM)measurements suggest that the latter is also associated with a crystal–liquid crystal(LC)phase transition at high temperatures.Together,these results provide the prerequisites for potential applications of bistable SCO molecules in spintronic devices and liquid crystal displays.
文摘In the domain of high-performance engineering polymers, the enhancement of mechanical flexibility in poly(phenylene sulfide) (PPS) resins has long posed a significant challenge. A novel molecular structure, designated as PP-He-IS, wherein imide rings and an aliphatic hexylene chain are covalently incorporated into the PPS backbone to enhance its flexibility, is introduced in this study. Molecular dynamics (MD) simulations are employed to systematically explore the effects of diversifying the backbone chain structures by substituting phenyl units with alkyl chains of varying lengths, referred to as PP-A-IS where “A” signifies the distinct intermediary alkyl chain configurations. Computational analyses reveal a discernable decrement in the glass transition temperature (Tg) and elastic modulus, counterbalanced by an increment in yield strength as the alkyl chain length is extended. Notably, the PP-He-IS variant is shown to exhibit superior yield strength while simultaneously maintaining reduced elastic modulus and Tg values, positioning it as an advantageous candidate for flexible PPS applications. Mesoscopic analyses further indicate that structures such as PP-He-IS, PP-Pe-IS, and PP-Bu-IS manifest remarkable flexibility, attributable to the presence of freely rotatable carbon-carbon single bonds. Experimental validation confirms that a melting temperature of 504 K which is lower than that of conventional PPS, and lower crystallinity are exhibited by PP-He-IS, thereby affording enhanced processability without compromising inherent thermal stability. Novel insights into the strategic modification of PPS for mechanical flexibility are thus furnished by this study, which also accentuates the pivotal role played by molecular dynamics simulations in spearheading high-throughput investigations in polymer material modifications.
基金Slovak grant agencies(APVV-19-0087,APVV-22-0172,DS-FR-22-0010 and VEGA 1/0029/22)are acknowledged for the financial support.J.J.,I.N.V.T.S.I.Š.acknowledge the financial support from the Grant Agency of the Czech Republic grant no.22-23760S+4 种基金This article was written with the generous support under the Operational Program Integrated Infrastructure for the project:“Strategic Research in the Field of SMART Monitoring,Treatment and Preventive Protection against Coronavirus(SARS-CoV-2)”project no.313011ASS8co-financed by the European Regional Development Fund.J.J.acknowledges financial support from an internal grant from Brno University of Technology CEITEC VUT-J-22-8049Furthermore,we acknowledge CzechNanoLab Research Infrastructure supported by MEYS CR(LM2023051)O.F.F.,I.N.and R.H.acknowledge the financial support from the institutional sources of the Department of Inorganic Chemistry,PalackýUniversity Olomouc,Czech Republic.O.F.F.acknowledges the support of MSTC Danube 8X23030 project.
文摘Two novel hexacoordinated Co(II)-based single-ion magnets were prepared and characterised.Both neutral complexes feature metal-centred coordination with one terminal and one bidentate nitrate anions along with tridentate derivatives of a 2,6-bis(1H-benzimidazole-2-yl)pyridine ligand containing either n-octyl(complex 1)or n-dodecyl(complex 2)chains.The presence of long aliphatic chains ensures their solubility in low polarity and volatile solvents frequently used for lithography patterning.This enabled the preparation of microstructural layers and patterns on technologically relevant substrates by easy-tohandle and low-cost wet lithographic techniques.On the other hand,attempts at surface deposition via sublimation were not successful due to thermal instability.
基金gotapproval from the Institutional Animal Ethical Care Committee(IAEC)of Shenyang Pharmaceutical University(ethical code:SYPU-IACUC-2022-0302-010).
文摘The clinical utility of irinotecan is restricted by individual variability in carboxylesterase expression.Direct administration of its active metabolite,7-ethyl-10-hydroxycamptothecin(SN38),presents an appealing alternative due to its potent anti-tumor efficacy.However,the undesirable properties of SN38,such as poor water solubility and nontarget toxicity,present significant hurdles to its clinical development.Prodrug nanoassemblies based on modular design strategy show promise in overcoming these challenges by enhancing drug delivery and selective activation.In modular design,the modification module plays a crucial role in improving the self-assembly capability of prodrugs.While current studies mainly focus on using straight aliphatic chains for prodrug design,branched aliphatic chains emerge as superior alternatives warranting further investigation.In this study,we selected 2-heptylundecanol(BAlc18)as modification module to construct an SN38 prodrug.Through exquisite design,SN38-SS-BAlc18 NPs integrated prominent properties in selfassembly capability,specific activation and biocompatibility,resolving the challenges of irinotecan and SN38,ultimately demonstrating excellent anti-tumor efficacy.This exploration enriched the design theory of prodrug nanoassemblies that can effectively balance safety and colorectal anti-tumor efficacy.
