Synthetic hydrogels with attractive mechanical strength and self-healing are particular appealing,in light of their significance and prospects in industrial,engineering and biomimetic fields.Fabricating various mechan...Synthetic hydrogels with attractive mechanical strength and self-healing are particular appealing,in light of their significance and prospects in industrial,engineering and biomimetic fields.Fabricating various mechanically robust and self-healable hydrogels have achieved some successes in using strong covalently bonded organic polymers as building blocks.However,creation of such soft materials entirely building on rigid inorganic components remains greatly challenging,because inorganic materials are usually poorly flexible and processable.In this study,mechanical robustness and self-recovery are successfully integrated into a single-component colloidal hydrogel system of aluminium hydroxide nanosheets(AHNSs).The inorganic colloidal hydrogel gains an excellent elasticity and stiffness,as indicated by its elastic modulus>10 MPa,due to the use of tough AHNS gelator and the formation of long-range ordered lamellar architectures consisting of self-assembled side-to-side or interlaced-stacking NS superstructures.The metastability in internal gel network endows the hydrogel a self-healing efficiency of larger than 100%.The AHNS hydrogel has been demonstrated to be effectively lubricative and anti-corrosive.Its mechanical,tribological and anticorrosion properties can be optimized by tuning its internal NS configuration and salt content.Our study may be a potent replenishment to the scope of materials science and may provide new insights into nanotechnology,colloidal chemistry,green tribology and mechanical engineering.展开更多
Variation of the surface adhesion force during the formation of octadecyl trichlorosilane (OTS) self-assembled monolayer on a glass substrate surface was investigated by atomic force microscope (AFM). The research sho...Variation of the surface adhesion force during the formation of octadecyl trichlorosilane (OTS) self-assembled monolayer on a glass substrate surface was investigated by atomic force microscope (AFM). The research shows that the hydrophobicity and the adhesion force of the sample surface increases gradually while the substrate surface is covered by OTS molecules as the reaction proceeds. After 15min reaction, a close-packed and smooth OTS self-assembled monolayer could form on the glass substrate surface with an advancing contact angle of 105° and an interfacial energy of 55.79mJ·m-2.展开更多
A new porphyrin-fluorescein hybrid 2 (Fl-PPTPP) has been synthesized and characterized by UV-Vis, IR, H-NMR, ESI-MS and elemental analysis. The supramolecular 1 self-assembly of Fl-PPTPP with amino-porphyrinatomangane...A new porphyrin-fluorescein hybrid 2 (Fl-PPTPP) has been synthesized and characterized by UV-Vis, IR, H-NMR, ESI-MS and elemental analysis. The supramolecular 1 self-assembly of Fl-PPTPP with amino-porphyrinatomanganese [Mn (p-APTPP)Cl] by hydrogen-bonding was studied using fluorescence spectroscopic titration and ESI-MS.展开更多
This paper describes the design, synthesis and characterization of a hydrogen-bonded molecular duplex with 1,8-naphthalimide fluorescent pendants. The two oligoamide molecular strands, with complementary hydrogen bond...This paper describes the design, synthesis and characterization of a hydrogen-bonded molecular duplex with 1,8-naphthalimide fluorescent pendants. The two oligoamide molecular strands, with complementary hydrogen bond sequences of DDADAA and AADADD, can form an ultra stable self-assembly duplex. Its molecular structure was confu-med by ^1H NMR and ESI-MS, and its photoluminescence properties were determined. The resulting duplex exhibited a dramatically enhanced photoluminescence （PL） quantum efficiency of 63.7% compared to the corresponding 1,8-naphthalimide segment （32.4%）, suggesting that the formation of the duplex with larger molecular weight could successfully inhibit the quenching of the fluorescent pendant. This novel duplex is a prospective candidate for new electroluminescent emitter.展开更多
Four 2,5-dialkoxylphenyl-l,3,4-oxadiazoles are shown to be efficient organogelators. These com- pounds readily form stable gels in many organic solvents and their gelation property as well as supramolecular structures...Four 2,5-dialkoxylphenyl-l,3,4-oxadiazoles are shown to be efficient organogelators. These com- pounds readily form stable gels in many organic solvents and their gelation property as well as supramolecular structures were investigated by scanning electron microscopy （SEM）, X-ray diffraction （XRD）, 1H nuclear magnetic resonance （1H NMR）, and ultraviolet-visible spectroscopy （UV-vis）. The results indicate that the gelator molecules self-assemble into gels with elongated fibrous networks and layer structures, and van der Waals interaction is the main driving force.展开更多
Nowadays,cancer has become the leading cause of death worldwide,driving the need for effective therapeutics to improve patient prognosis.Photodynamic therapy(PDT)has been widely applied as an antitumor modality,owing ...Nowadays,cancer has become the leading cause of death worldwide,driving the need for effective therapeutics to improve patient prognosis.Photodynamic therapy(PDT)has been widely applied as an antitumor modality,owing to its minimal invasiveness,localized tumor damage,and high safety profile.However,its efficacy is limited by poor stability of photosensitizers,inadequate tumor accumulation,and a complex tumor microenvironment.To overcome these challenges,extensive endeavors have been made to explore the co-assembly of the widely used photosensitizer chlorin e6(Ce6)with various functional small molecules to enhance pharmacodynamic activity.This review provides a comprehensive overview of current studies on Ce6-based nanoparticles for effective PDT and precise delivery of functional molecules.The self-assembly mechanism will be discussed in detail,with a focus on potential strategies for combinational therapy with PDT.展开更多
Photothermal conversion is one of the key technologies in solar energy collection,seawater desalination,photo thermal treatment and other important fields.In order to develop next generation photothermal materials,fou...Photothermal conversion is one of the key technologies in solar energy collection,seawater desalination,photo thermal treatment and other important fields.In order to develop next generation photothermal materials,four poly oxometalates,[(CH_(3))_(2)NH_(2)]_(12)H_(5)[Ni_(3)Mo_(18)O_(54)(HPO_(3))_(10)(PO_(4))]·_(18)H_(2)O(Compound 1),[(CH_(3))_(2)NH_(2)]_(1)Na_(11)[Ni_(2)Mo_(8)O_(22)(HPO_(3))_(10)]·16H_(2)O(Compound 2),Na_(15)(OH)_5[Mo_(6)O_(18)(HPO_(3))_(4)]_(2)[MoO]_(1.5)·16H_(2)O(Compound 3),[(CH_(3))_(2)NH_(2)]_(4)Na_(11)[Na[Mo_6O_(15)(HPO_(3))_(4)]_(2)]·_(18)H_(2)O(Compound 4),are successfully designed and synthesized via a micro wave-as sis ted reaction protocol.Compounds 1-4 not only exhibit broad absorption and notable photothermal conversion effects in near-infrared(NIR)region,but also have high photothermal conversion efficiencies and high quality NIR photothermal imaging effects under NIR laser irradiation.Compound 1 shows the best photothermal conversion effect,and it provides a unique model to explore the relationship between the complex metal oxide structure and photothermal conversion behavior at the molecular level.Both the experimental results and theoretical calculations consistently conclude that the charge and degree of electron delocalization on the Cluster have a robust influence on the photothermal conversion,as well as the aggregation microstructures.展开更多
Silver(Ag) nanostructures demonstrate outstanding optical, electrical, magnetic, and catalytic properties and are utilized in photonic, energy, sensors, and biomedical devices.The target application and the performanc...Silver(Ag) nanostructures demonstrate outstanding optical, electrical, magnetic, and catalytic properties and are utilized in photonic, energy, sensors, and biomedical devices.The target application and the performance can be inherently tuned by control of configuration, shape, and size of Ag nanostructures. In this work, we demonstrate the systematical fabrication of various configurations of Ag nanostructures on sapphire(0001) by controlling the Ag deposition thickness at different annealing environments in a plasma ion coater. In particular, the evolution of Ag particles(between 2 and 20 nm),irregular nanoclusters(between 30 and 60 nm), and nanocluster networks(between 80 and 200 nm) are found be depended on the thickness of Ag thin film. The results were systematically analyzed and explained based on the solid-state dewetting,surface diffusion, Volmer–Weber growth model, coalescence,and surface energy minimization mechanism. The growth behavior of Ag nanostructures is remarkably differentiated at higher annealing temperature(750 ℃) due to the sublimation and temperature-dependent characteristic of dewetting process.In addition, Raman and reflectance spectra analyses reveal that optical properties of Ag nanostructures depend on their morphology.展开更多
Metallo-supramolecular chemistry based on the reversible,directional,and predictable noncovalent interaction of metal–ligand coordination has been widely applied in constructing a myriad of two-and threedimensional s...Metallo-supramolecular chemistry based on the reversible,directional,and predictable noncovalent interaction of metal–ligand coordination has been widely applied in constructing a myriad of two-and threedimensional supramolecules with sophisticated structures.The development of metallo-supramolecular chemistry highly relies on facile characterization methods.For advancement of structural complexity with desired functions,however,conventional crystallographicandspectroscopiccharacterizationsarelimited by crystal growth,sample purity,and severe signal overlaps.With high sensitivity and low requirement for purity,multidimensional mass spectrometry(MS),including electrospray ionization-MS(ESI-MS),tandem MS(MS2),and ion mobility-MS(IM-MS),is emerging as an essential analytical tool for characterization of the chemical compositions,connectivity,stability,shape,and size of metallo-supramolecules,as well as kinetic and thermodynamic features of self-assembly processes.Thus,this review mainly focuses on the recentdevelopment ofmultidimensionalMSinmetallosupramolecular characterization and discusses how ESI-MS,MS2,and IM-MS assist the development of metallo-supramolecular chemistry.展开更多
A gold electrode covered with selfassembled monolayers of 2mercaptobenzothiazole(Au/MBT)has been developed and its electrochemical characteristics have been investigated in detail.Using hexacyanoferrate as the electro...A gold electrode covered with selfassembled monolayers of 2mercaptobenzothiazole(Au/MBT)has been developed and its electrochemical characteristics have been investigated in detail.Using hexacyanoferrate as the electrochemical probe for studying the characteristics of the MBT monolayer film,the results,obtained by A.C.impedance spectroscopy technique,show that the electron transfer of hexacyanoferrate()on Au|MBT in higher pH media was more difficult than that obtained in H2SO4 medium or on a bare gold electrode.The electrochemical reversibility of Fe(CN)3-6/Fe(CN)4-6 changed with pH of the solution due to the proton and deproton states of N atom of MBT.The relationship between the coverage of MBT on Au surface or pH and the apparent heterogeneous rate constant was derived and discussed.The double layer capacitance of Au|MBT is(76455)F/cm2.The characteristic frequency was dependent on the pH of the solution.展开更多
Advances in nanotechnology depend upon expanding the ability to create biologically inspired complex materials with well-defined multidimensional structures.Fabrication of hybrid hierarchical structures by combining c...Advances in nanotechnology depend upon expanding the ability to create biologically inspired complex materials with well-defined multidimensional structures.Fabrication of hybrid hierarchical structures by combining colloidal organic and inorganic building blocks remains a challenge due to the difficulty in preparing a diverse spectrum of rigid-flexible coupling units of precise shape and size.Herewe reportageneral strategy for crafting amyriad of uniform aggregates via manipulating self-assembly of distinct dendimers with precisely controlled polyhed raloligomeric silse squioxane(POSS)-embedded cores integrating stiffness and ductility.The rigidity of POSS units exerts steric effects onself-amplification of hydrophobic do mains while the flexibility from internally ductile linkages provides ideal scenarios in establishing self-adaptive structural optimization,which subsequently drive the assemblies to proceed into hierarchical self-assembly via multiple coordination effects,generating highly complex multi compartment micelles(MCMs)without any preprocessing.Our facile approach enables a robust modular nanofabrication of well-organized dendrimers toward artificial functional systems with defined geometric architectures and intriguing functions for advanced biological applications.展开更多
基金This work is financially supported by Special Talents Program of Lanzhou Institute of Chemical Physics(No.E0SX0282)Shandong Laboratory Program(No.E1R06SXM07).
文摘Synthetic hydrogels with attractive mechanical strength and self-healing are particular appealing,in light of their significance and prospects in industrial,engineering and biomimetic fields.Fabricating various mechanically robust and self-healable hydrogels have achieved some successes in using strong covalently bonded organic polymers as building blocks.However,creation of such soft materials entirely building on rigid inorganic components remains greatly challenging,because inorganic materials are usually poorly flexible and processable.In this study,mechanical robustness and self-recovery are successfully integrated into a single-component colloidal hydrogel system of aluminium hydroxide nanosheets(AHNSs).The inorganic colloidal hydrogel gains an excellent elasticity and stiffness,as indicated by its elastic modulus>10 MPa,due to the use of tough AHNS gelator and the formation of long-range ordered lamellar architectures consisting of self-assembled side-to-side or interlaced-stacking NS superstructures.The metastability in internal gel network endows the hydrogel a self-healing efficiency of larger than 100%.The AHNS hydrogel has been demonstrated to be effectively lubricative and anti-corrosive.Its mechanical,tribological and anticorrosion properties can be optimized by tuning its internal NS configuration and salt content.Our study may be a potent replenishment to the scope of materials science and may provide new insights into nanotechnology,colloidal chemistry,green tribology and mechanical engineering.
基金Partially supported by Scientific Research Foundation for Returned Overseas Chinese Scholars,State Education Committee.
文摘Variation of the surface adhesion force during the formation of octadecyl trichlorosilane (OTS) self-assembled monolayer on a glass substrate surface was investigated by atomic force microscope (AFM). The research shows that the hydrophobicity and the adhesion force of the sample surface increases gradually while the substrate surface is covered by OTS molecules as the reaction proceeds. After 15min reaction, a close-packed and smooth OTS self-assembled monolayer could form on the glass substrate surface with an advancing contact angle of 105° and an interfacial energy of 55.79mJ·m-2.
基金We are gratefully acknowledged financial support of this work by the National Natural ScienceFoundation of China (2007 1034) the N.S.F of Guangdong Province of China.
文摘A new porphyrin-fluorescein hybrid 2 (Fl-PPTPP) has been synthesized and characterized by UV-Vis, IR, H-NMR, ESI-MS and elemental analysis. The supramolecular 1 self-assembly of Fl-PPTPP with amino-porphyrinatomanganese [Mn (p-APTPP)Cl] by hydrogen-bonding was studied using fluorescence spectroscopic titration and ESI-MS.
基金This project was financially supported by the National Natural Science Foundation of China(Grant No.20102004).
文摘This paper describes the design, synthesis and characterization of a hydrogen-bonded molecular duplex with 1,8-naphthalimide fluorescent pendants. The two oligoamide molecular strands, with complementary hydrogen bond sequences of DDADAA and AADADD, can form an ultra stable self-assembly duplex. Its molecular structure was confu-med by ^1H NMR and ESI-MS, and its photoluminescence properties were determined. The resulting duplex exhibited a dramatically enhanced photoluminescence （PL） quantum efficiency of 63.7% compared to the corresponding 1,8-naphthalimide segment （32.4%）, suggesting that the formation of the duplex with larger molecular weight could successfully inhibit the quenching of the fluorescent pendant. This novel duplex is a prospective candidate for new electroluminescent emitter.
文摘Four 2,5-dialkoxylphenyl-l,3,4-oxadiazoles are shown to be efficient organogelators. These com- pounds readily form stable gels in many organic solvents and their gelation property as well as supramolecular structures were investigated by scanning electron microscopy （SEM）, X-ray diffraction （XRD）, 1H nuclear magnetic resonance （1H NMR）, and ultraviolet-visible spectroscopy （UV-vis）. The results indicate that the gelator molecules self-assemble into gels with elongated fibrous networks and layer structures, and van der Waals interaction is the main driving force.
基金National Natural Science Foundation of China,Grant/Award Number:82222903Li Ka Shing Faculty of Medicine(Start-up Fund)of The University of Hong Kong.
文摘Nowadays,cancer has become the leading cause of death worldwide,driving the need for effective therapeutics to improve patient prognosis.Photodynamic therapy(PDT)has been widely applied as an antitumor modality,owing to its minimal invasiveness,localized tumor damage,and high safety profile.However,its efficacy is limited by poor stability of photosensitizers,inadequate tumor accumulation,and a complex tumor microenvironment.To overcome these challenges,extensive endeavors have been made to explore the co-assembly of the widely used photosensitizer chlorin e6(Ce6)with various functional small molecules to enhance pharmacodynamic activity.This review provides a comprehensive overview of current studies on Ce6-based nanoparticles for effective PDT and precise delivery of functional molecules.The self-assembly mechanism will be discussed in detail,with a focus on potential strategies for combinational therapy with PDT.
基金financially supported by the Natural Science Foundation of Hunan Province(No.2020JJ4684)the Fundamental Research Funds for the Central Universities of Central South University(No.2021zzts0522)+1 种基金the Recruitment Program of Global Youth Expertsthe Open Project of the Key Laboratory of Digital Flavor Research of Hunan China Tobacco Industry Co.,Ltd(No.202143000834024)。
文摘Photothermal conversion is one of the key technologies in solar energy collection,seawater desalination,photo thermal treatment and other important fields.In order to develop next generation photothermal materials,four poly oxometalates,[(CH_(3))_(2)NH_(2)]_(12)H_(5)[Ni_(3)Mo_(18)O_(54)(HPO_(3))_(10)(PO_(4))]·_(18)H_(2)O(Compound 1),[(CH_(3))_(2)NH_(2)]_(1)Na_(11)[Ni_(2)Mo_(8)O_(22)(HPO_(3))_(10)]·16H_(2)O(Compound 2),Na_(15)(OH)_5[Mo_(6)O_(18)(HPO_(3))_(4)]_(2)[MoO]_(1.5)·16H_(2)O(Compound 3),[(CH_(3))_(2)NH_(2)]_(4)Na_(11)[Na[Mo_6O_(15)(HPO_(3))_(4)]_(2)]·_(18)H_(2)O(Compound 4),are successfully designed and synthesized via a micro wave-as sis ted reaction protocol.Compounds 1-4 not only exhibit broad absorption and notable photothermal conversion effects in near-infrared(NIR)region,but also have high photothermal conversion efficiencies and high quality NIR photothermal imaging effects under NIR laser irradiation.Compound 1 shows the best photothermal conversion effect,and it provides a unique model to explore the relationship between the complex metal oxide structure and photothermal conversion behavior at the molecular level.Both the experimental results and theoretical calculations consistently conclude that the charge and degree of electron delocalization on the Cluster have a robust influence on the photothermal conversion,as well as the aggregation microstructures.
基金the National Research Foundation of Korea(no.2011-0030079 and 2016R1A1A1A05005009)the research grant of Kwangwoon University in 2016
文摘Silver(Ag) nanostructures demonstrate outstanding optical, electrical, magnetic, and catalytic properties and are utilized in photonic, energy, sensors, and biomedical devices.The target application and the performance can be inherently tuned by control of configuration, shape, and size of Ag nanostructures. In this work, we demonstrate the systematical fabrication of various configurations of Ag nanostructures on sapphire(0001) by controlling the Ag deposition thickness at different annealing environments in a plasma ion coater. In particular, the evolution of Ag particles(between 2 and 20 nm),irregular nanoclusters(between 30 and 60 nm), and nanocluster networks(between 80 and 200 nm) are found be depended on the thickness of Ag thin film. The results were systematically analyzed and explained based on the solid-state dewetting,surface diffusion, Volmer–Weber growth model, coalescence,and surface energy minimization mechanism. The growth behavior of Ag nanostructures is remarkably differentiated at higher annealing temperature(750 ℃) due to the sublimation and temperature-dependent characteristic of dewetting process.In addition, Raman and reflectance spectra analyses reveal that optical properties of Ag nanostructures depend on their morphology.
基金X.L.acknowledges the support from the Developmental Fund for Science and Technology of Shenzhen government(grant no.RCJC20200714114556036)Tencent Funders Alumni Foundation.H.W.thanks the support from the National Natural Science Foundation of China(no.22001176).
文摘Metallo-supramolecular chemistry based on the reversible,directional,and predictable noncovalent interaction of metal–ligand coordination has been widely applied in constructing a myriad of two-and threedimensional supramolecules with sophisticated structures.The development of metallo-supramolecular chemistry highly relies on facile characterization methods.For advancement of structural complexity with desired functions,however,conventional crystallographicandspectroscopiccharacterizationsarelimited by crystal growth,sample purity,and severe signal overlaps.With high sensitivity and low requirement for purity,multidimensional mass spectrometry(MS),including electrospray ionization-MS(ESI-MS),tandem MS(MS2),and ion mobility-MS(IM-MS),is emerging as an essential analytical tool for characterization of the chemical compositions,connectivity,stability,shape,and size of metallo-supramolecules,as well as kinetic and thermodynamic features of self-assembly processes.Thus,this review mainly focuses on the recentdevelopment ofmultidimensionalMSinmetallosupramolecular characterization and discusses how ESI-MS,MS2,and IM-MS assist the development of metallo-supramolecular chemistry.
文摘A gold electrode covered with selfassembled monolayers of 2mercaptobenzothiazole(Au/MBT)has been developed and its electrochemical characteristics have been investigated in detail.Using hexacyanoferrate as the electrochemical probe for studying the characteristics of the MBT monolayer film,the results,obtained by A.C.impedance spectroscopy technique,show that the electron transfer of hexacyanoferrate()on Au|MBT in higher pH media was more difficult than that obtained in H2SO4 medium or on a bare gold electrode.The electrochemical reversibility of Fe(CN)3-6/Fe(CN)4-6 changed with pH of the solution due to the proton and deproton states of N atom of MBT.The relationship between the coverage of MBT on Au surface or pH and the apparent heterogeneous rate constant was derived and discussed.The double layer capacitance of Au|MBT is(76455)F/cm2.The characteristic frequency was dependent on the pH of the solution.
基金This work was supported by NSFC(nos.51973226,21725403,51803188,and 21504096),the Ministry of Science and Technology of China(no.2014CB932200),and the China Postdoctoral Science Foundation(nos.2018M642783 and 2019T120636).
文摘Advances in nanotechnology depend upon expanding the ability to create biologically inspired complex materials with well-defined multidimensional structures.Fabrication of hybrid hierarchical structures by combining colloidal organic and inorganic building blocks remains a challenge due to the difficulty in preparing a diverse spectrum of rigid-flexible coupling units of precise shape and size.Herewe reportageneral strategy for crafting amyriad of uniform aggregates via manipulating self-assembly of distinct dendimers with precisely controlled polyhed raloligomeric silse squioxane(POSS)-embedded cores integrating stiffness and ductility.The rigidity of POSS units exerts steric effects onself-amplification of hydrophobic do mains while the flexibility from internally ductile linkages provides ideal scenarios in establishing self-adaptive structural optimization,which subsequently drive the assemblies to proceed into hierarchical self-assembly via multiple coordination effects,generating highly complex multi compartment micelles(MCMs)without any preprocessing.Our facile approach enables a robust modular nanofabrication of well-organized dendrimers toward artificial functional systems with defined geometric architectures and intriguing functions for advanced biological applications.
