The efficacy of chemotherapeutic drug in cancer treatment is often hampered by drug resistance of tumor cells,which is usually caused by abnormal gene expression.RNA interference mediated by si RNA and mi RNA can sele...The efficacy of chemotherapeutic drug in cancer treatment is often hampered by drug resistance of tumor cells,which is usually caused by abnormal gene expression.RNA interference mediated by si RNA and mi RNA can selectively knock down the carcinogenic genes by targeting specific m RNAs.Therefore,combining chemotherapeutic drugs with gene agents could be a promising strategy for cancer therapy.Due to poor stability and solubility associated with gene agents and drugs,suitable protective carriers are needed and have been widely researched for the co-delivery.In this review,we summarize the most commonly used nanocarriers for co-delivery of chemotherapeutic drugs and gene agents,as well as the advances in co-delivery systems.展开更多
A gel based on polyacrylamide,exhibiting delayed crosslinking characteristics,emerges as the preferred solution for mitigating degradation under conditions of high temperature and extended shear in ultralong wellbores...A gel based on polyacrylamide,exhibiting delayed crosslinking characteristics,emerges as the preferred solution for mitigating degradation under conditions of high temperature and extended shear in ultralong wellbores.High viscosity/viscoelasticity of the fracturing fluid was required to maintain excellent proppant suspension properties before gelling.Taking into account both the cost and the potential damage to reservoirs,polymers with lower concentrations and molecular weights are generally preferred.In this work,the supramolecular action was integrated into the polymer,resulting in significant increases in the viscosity and viscoelasticity of the synthesized supramolecular polymer system.The double network gel,which is formed by the combination of the supramolecular polymer system and a small quantity of Zr-crosslinker,effectively resists temperature while minimizing permeability damage to the reservoir.The results indicate that the supramolecular polymer system with a molecular weight of(268—380)×10^(4)g/mol can achieve the same viscosity and viscoelasticity at 0.4 wt%due to the supramolecular interaction between polymers,compared to the 0.6 wt%traditional polymer(hydrolyzed polyacrylamide,molecular weight of 1078×10^(4)g/mol).The supramolecular polymer system possessed excellent proppant suspension properties with a 0.55 cm/min sedimentation rate at 0.4 wt%,whereas the0.6 wt%traditional polymer had a rate of 0.57 cm/min.In comparison to the traditional gel with a Zrcrosslinker concentration of 0.6 wt%and an elastic modulus of 7.77 Pa,the double network gel with a higher elastic modulus(9.00 Pa)could be formed only at 0.1 wt%Zr-crosslinker,which greatly reduced the amount of residue of the fluid after gel-breaking.The viscosity of the double network gel was66 m Pa s after 2 h shearing,whereas the traditional gel only reached 27 m Pa s.展开更多
Ethyl cellulose(EC),an important biomass-based material,has excellent film-forming properties.Nevertheless,the high interchain hydrogen bond interaction leads to a high glass transition temperature of EC,which makes i...Ethyl cellulose(EC),an important biomass-based material,has excellent film-forming properties.Nevertheless,the high interchain hydrogen bond interaction leads to a high glass transition temperature of EC,which makes it too brittle to be used widely.The hydroxyl group on EC can form a supramolecular system in the form of a non-covalent bond with an effective plasticizer.In this study,an important vegetable-oil-based derivative named dimer fatty acid was used to prepare a novel special plasticizer for EC.Dimer-fatty-acid-based thioether polyol(DATP)was synthesized and used to modify ethyl cellulose films.The supramolecular composite films of DATP and ethyl cellulose were designed using the newly-formed van der Waals force.The thermal stability,morphology,hydrophilicity,and mechanical properties of the composite films were all tested.Pure EC is fragile,and the addition of DATP makes the ethyl cellulose films more flexible.The elongation at the break of EC supramolecular films increased and the tensile strength decreased with the increasing DATP content.The elongation at the break of EC/DATP(60/40)and EC/DATP(50/50)was up to 40.3%and 43.4%,respectively.Noticeably,the thermal initial degradation temperature of the film with 10%DATP is higher than that of pure EC,which may be attributed to the formation of a better supramolecular system in this composite film.The application of bio-based material(EC)is environmentally friendly,and the novel DATP can be used as a special and effective plasticizer to prepare flexible EC films,making it more widely used in energy,chemical industry,materials,agriculture,medicine,and other fields.展开更多
In this work,we have designed and synthesized a cyano-substituted p-phenylenevinylene derivative(PPTA),which can self-assemble into positively charged nanoparticles in an aqueous solution with a deep green fluorescenc...In this work,we have designed and synthesized a cyano-substituted p-phenylenevinylene derivative(PPTA),which can self-assemble into positively charged nanoparticles in an aqueous solution with a deep green fluorescence.An anionic polyelectrolyte material guar gum modified by carboxylic acid(GP5A)was chosen to build an artificial light-harvesting system(LHS)through self-assembly with PPTA,in which two acceptors Eosin Y(EY)and Nile red(NiR)were loaded into the PPTA-GP5A assemblies through electrostatic interaction and Van der Waals force.By adjusting the molar ratio of PPTA-GP5A/EY at 1:0.004,the one-step artificial LHS can exhibit high energy transfer efficiency(Φ_(ET))(38.9%)and antenna effect(AE)(4.6).Subsequently,with the addition of NiR,theΦET and AE of the two-step sequential artificial LHS were calculated to be 71.9%and 13.5,respectively.Moreover,the two-step artificial LHS constructed by the polyelectrolyte material GP5A can be used as a nanoreactor to photocatalyst alkylation of C-H bonds of phenyl vinyl sulfone(PVS)and tetrahydrofuran(THF)in water with a yield of 42%.Therefore,we have constructed an artificial LHS with two-step energy transfer based on polyelectrolytes through the electrostatic interaction to improve energy transfer efficiency,which can also be used as a nanoreactor for photocatalysis.展开更多
In this work, a UV-Visible light controlled supramolecular system based on ethyl cellulose （EC） was constructed, combining the host-guest interaction of β-cyclodextrin （β-CD） group and trans-isomer of azobenzene...In this work, a UV-Visible light controlled supramolecular system based on ethyl cellulose （EC） was constructed, combining the host-guest interaction of β-cyclodextrin （β-CD） group and trans-isomer of azobenzene （tAzo） group. To link β-CD to the hydrophobic section, renewable EC was used as macroinitiator to initiate the polymerization of ε-caprolactone （ε-CL） to form biocompatible and biodegradable comb copolymer EC-g-PCL, and β-CD was attached to the end of PCL side chain via click reaction. Meanwhile, hydrophilic PEG-tAzo was obtained by N,N＇-dicyclohexylcarbodiimide （DCC） coupling. Then, the structures of the products were characterized by nuclear magnetic resonance （NMR） and gel permeation chromatography （GPC）. Subsequently, with the formation of inclusion complexes by β-CD and tAzo groups, the obtained EC-g-PCL-β-CD/PEG-tAzo supramolecular system self-assembled in water with hydrophobic EC-g-PCL-β-CD as core and hydrophilic PEG-tAzo as shell. Furthermore, dynamic light scattering （DLS） and transmission electron microscopy （TEM） were utilized to investigate the particle size and size distribution, while NMR and UV-Vis spectra were applied to explore the UV-Visible light stimuli-responsiveness of the micelles.展开更多
The solutions of rare earth complexes Sm(Phen) 2(TTA)(Bipy)(NO 3) 3 and Sm(L) x (TTA) 4-x (NO 3) 3 [L=Phen (1,10-phenanthroline) or Bipy(2,2′-bipyridine), x =4, 3, 2, 1, 0; TTA is 2-thenoyltrifluoacetone] in EtOH(1&#...The solutions of rare earth complexes Sm(Phen) 2(TTA)(Bipy)(NO 3) 3 and Sm(L) x (TTA) 4-x (NO 3) 3 [L=Phen (1,10-phenanthroline) or Bipy(2,2′-bipyridine), x =4, 3, 2, 1, 0; TTA is 2-thenoyltrifluoacetone] in EtOH(1×10 -3 mol/L) were prepared. The coefficients of antenna effect are 31 5, 18 2 and 5 6 for Phen, Bipy and TTA, respectively, when the electron configuration of the excited state of the samarium atom in the complexes is 4 D 1/2 . The fluorescent intensity and the lifetime of the supramolecular encapsulation products of (CH 3) 3Si-MCM-41 and Sm 3+ complexes are stronger and longer than those of the encapsulation products of MCM-41 and Sm 3+ complexes respectively. The results show that the host with lipophilic channels is more favourable to the fluorescence of the rare earth complexes than the hydrophilic mesoporous molecular sieve. The fluorescent intensity of (CH 3) 3Si-MCM-41-Sm(Phen) 3(TTA)(NO 3) 3 is the strongest \{among\} the encapsulation series of Sm 3+ complexes, which is assumed to result from the greatly reduction of SiO-H vibration relaxation in host (CH 3) 3Si-MCM-41 and the presence of the discrete strong luminescent centres of the guest molecules associated with the nanosized material′s structure. The luminescent decay halftime of the supramolecular materials is much shorter than that of the powder of the samarium complexes. The result shows that the ligand transferring energy from the triplet state to the singlet state of Sm 3+ ( T 1→S , intersystem crossing) becomes higher. The fluorescent experimental results indicate that the interaction between the host and the guest influences the luminescent properties of the nanostructured supramolecular materials.展开更多
基金supported by the National Natural Science Foundation of China (No.81373342)Beijing Natural Science Foundation (Nos.2141004 and 7142114)
文摘The efficacy of chemotherapeutic drug in cancer treatment is often hampered by drug resistance of tumor cells,which is usually caused by abnormal gene expression.RNA interference mediated by si RNA and mi RNA can selectively knock down the carcinogenic genes by targeting specific m RNAs.Therefore,combining chemotherapeutic drugs with gene agents could be a promising strategy for cancer therapy.Due to poor stability and solubility associated with gene agents and drugs,suitable protective carriers are needed and have been widely researched for the co-delivery.In this review,we summarize the most commonly used nanocarriers for co-delivery of chemotherapeutic drugs and gene agents,as well as the advances in co-delivery systems.
基金financially supported by the National Natural Science Foundation of China(Nos.52120105007 and 52374062)the Innovation Fund Project for Graduate Students of China University of Petroleum(East China)supported by“the Fundamental Research Funds for the Central Universities”(23CX04047A)。
文摘A gel based on polyacrylamide,exhibiting delayed crosslinking characteristics,emerges as the preferred solution for mitigating degradation under conditions of high temperature and extended shear in ultralong wellbores.High viscosity/viscoelasticity of the fracturing fluid was required to maintain excellent proppant suspension properties before gelling.Taking into account both the cost and the potential damage to reservoirs,polymers with lower concentrations and molecular weights are generally preferred.In this work,the supramolecular action was integrated into the polymer,resulting in significant increases in the viscosity and viscoelasticity of the synthesized supramolecular polymer system.The double network gel,which is formed by the combination of the supramolecular polymer system and a small quantity of Zr-crosslinker,effectively resists temperature while minimizing permeability damage to the reservoir.The results indicate that the supramolecular polymer system with a molecular weight of(268—380)×10^(4)g/mol can achieve the same viscosity and viscoelasticity at 0.4 wt%due to the supramolecular interaction between polymers,compared to the 0.6 wt%traditional polymer(hydrolyzed polyacrylamide,molecular weight of 1078×10^(4)g/mol).The supramolecular polymer system possessed excellent proppant suspension properties with a 0.55 cm/min sedimentation rate at 0.4 wt%,whereas the0.6 wt%traditional polymer had a rate of 0.57 cm/min.In comparison to the traditional gel with a Zrcrosslinker concentration of 0.6 wt%and an elastic modulus of 7.77 Pa,the double network gel with a higher elastic modulus(9.00 Pa)could be formed only at 0.1 wt%Zr-crosslinker,which greatly reduced the amount of residue of the fluid after gel-breaking.The viscosity of the double network gel was66 m Pa s after 2 h shearing,whereas the traditional gel only reached 27 m Pa s.
基金supported by Jiangsu Province Biomass Energy and Materials Laboratory,China(Grant No.JSBEM-S-202007).
文摘Ethyl cellulose(EC),an important biomass-based material,has excellent film-forming properties.Nevertheless,the high interchain hydrogen bond interaction leads to a high glass transition temperature of EC,which makes it too brittle to be used widely.The hydroxyl group on EC can form a supramolecular system in the form of a non-covalent bond with an effective plasticizer.In this study,an important vegetable-oil-based derivative named dimer fatty acid was used to prepare a novel special plasticizer for EC.Dimer-fatty-acid-based thioether polyol(DATP)was synthesized and used to modify ethyl cellulose films.The supramolecular composite films of DATP and ethyl cellulose were designed using the newly-formed van der Waals force.The thermal stability,morphology,hydrophilicity,and mechanical properties of the composite films were all tested.Pure EC is fragile,and the addition of DATP makes the ethyl cellulose films more flexible.The elongation at the break of EC supramolecular films increased and the tensile strength decreased with the increasing DATP content.The elongation at the break of EC/DATP(60/40)and EC/DATP(50/50)was up to 40.3%and 43.4%,respectively.Noticeably,the thermal initial degradation temperature of the film with 10%DATP is higher than that of pure EC,which may be attributed to the formation of a better supramolecular system in this composite film.The application of bio-based material(EC)is environmentally friendly,and the novel DATP can be used as a special and effective plasticizer to prepare flexible EC films,making it more widely used in energy,chemical industry,materials,agriculture,medicine,and other fields.
基金We are grateful for the financial support from the National Natural Science Foundation of China(Nos.52205210 and 22005179)the Natural Science Foundation of Shandong Province(Nos.ZR2020MB018,ZR2022QE033,ZR2020QB113 and ZR2018BEE015).
文摘In this work,we have designed and synthesized a cyano-substituted p-phenylenevinylene derivative(PPTA),which can self-assemble into positively charged nanoparticles in an aqueous solution with a deep green fluorescence.An anionic polyelectrolyte material guar gum modified by carboxylic acid(GP5A)was chosen to build an artificial light-harvesting system(LHS)through self-assembly with PPTA,in which two acceptors Eosin Y(EY)and Nile red(NiR)were loaded into the PPTA-GP5A assemblies through electrostatic interaction and Van der Waals force.By adjusting the molar ratio of PPTA-GP5A/EY at 1:0.004,the one-step artificial LHS can exhibit high energy transfer efficiency(Φ_(ET))(38.9%)and antenna effect(AE)(4.6).Subsequently,with the addition of NiR,theΦET and AE of the two-step sequential artificial LHS were calculated to be 71.9%and 13.5,respectively.Moreover,the two-step artificial LHS constructed by the polyelectrolyte material GP5A can be used as a nanoreactor to photocatalyst alkylation of C-H bonds of phenyl vinyl sulfone(PVS)and tetrahydrofuran(THF)in water with a yield of 42%.Therefore,we have constructed an artificial LHS with two-step energy transfer based on polyelectrolytes through the electrostatic interaction to improve energy transfer efficiency,which can also be used as a nanoreactor for photocatalysis.
基金financially supported by the National Natural Science Foundation of China(Nos.21174076 and 21374053)the Specialized Research Fund for the Doctoral Program of Higher Education of China(No.20120002110015)
文摘In this work, a UV-Visible light controlled supramolecular system based on ethyl cellulose （EC） was constructed, combining the host-guest interaction of β-cyclodextrin （β-CD） group and trans-isomer of azobenzene （tAzo） group. To link β-CD to the hydrophobic section, renewable EC was used as macroinitiator to initiate the polymerization of ε-caprolactone （ε-CL） to form biocompatible and biodegradable comb copolymer EC-g-PCL, and β-CD was attached to the end of PCL side chain via click reaction. Meanwhile, hydrophilic PEG-tAzo was obtained by N,N＇-dicyclohexylcarbodiimide （DCC） coupling. Then, the structures of the products were characterized by nuclear magnetic resonance （NMR） and gel permeation chromatography （GPC）. Subsequently, with the formation of inclusion complexes by β-CD and tAzo groups, the obtained EC-g-PCL-β-CD/PEG-tAzo supramolecular system self-assembled in water with hydrophobic EC-g-PCL-β-CD as core and hydrophilic PEG-tAzo as shell. Furthermore, dynamic light scattering （DLS） and transmission electron microscopy （TEM） were utilized to investigate the particle size and size distribution, while NMR and UV-Vis spectra were applied to explore the UV-Visible light stimuli-responsiveness of the micelles.
基金Supported by the Science Foundation of Guangzhou City( 2 0 0 0 - Z- 0 76 - 0 1),L aboratory of Rare Earth Chemistry andPhysics,Changchun Institution of Applied Chemistry,Chinese Academ y of Sciences and Key L aboratory of Inorganic Synthe-sis and Pr
文摘The solutions of rare earth complexes Sm(Phen) 2(TTA)(Bipy)(NO 3) 3 and Sm(L) x (TTA) 4-x (NO 3) 3 [L=Phen (1,10-phenanthroline) or Bipy(2,2′-bipyridine), x =4, 3, 2, 1, 0; TTA is 2-thenoyltrifluoacetone] in EtOH(1×10 -3 mol/L) were prepared. The coefficients of antenna effect are 31 5, 18 2 and 5 6 for Phen, Bipy and TTA, respectively, when the electron configuration of the excited state of the samarium atom in the complexes is 4 D 1/2 . The fluorescent intensity and the lifetime of the supramolecular encapsulation products of (CH 3) 3Si-MCM-41 and Sm 3+ complexes are stronger and longer than those of the encapsulation products of MCM-41 and Sm 3+ complexes respectively. The results show that the host with lipophilic channels is more favourable to the fluorescence of the rare earth complexes than the hydrophilic mesoporous molecular sieve. The fluorescent intensity of (CH 3) 3Si-MCM-41-Sm(Phen) 3(TTA)(NO 3) 3 is the strongest \{among\} the encapsulation series of Sm 3+ complexes, which is assumed to result from the greatly reduction of SiO-H vibration relaxation in host (CH 3) 3Si-MCM-41 and the presence of the discrete strong luminescent centres of the guest molecules associated with the nanosized material′s structure. The luminescent decay halftime of the supramolecular materials is much shorter than that of the powder of the samarium complexes. The result shows that the ligand transferring energy from the triplet state to the singlet state of Sm 3+ ( T 1→S , intersystem crossing) becomes higher. The fluorescent experimental results indicate that the interaction between the host and the guest influences the luminescent properties of the nanostructured supramolecular materials.
