An un precedented tun able hydrophobic effect in self-assembly of a small cationic organic fluorophore(NI-TPy^(+))-based with aggregation-induced emission(AIE)property was realized in aqueous solution.The amplificatio...An un precedented tun able hydrophobic effect in self-assembly of a small cationic organic fluorophore(NI-TPy^(+))-based with aggregation-induced emission(AIE)property was realized in aqueous solution.The amplification of hydrophobicity was found to be significantly dependent upon the increasing aggregates of NI-TPy^(+),which enabled the study of the hydrophobic binding of chaotropic anions with the Hofmeister series.展开更多
Salt influences protein stability through electrostatic mechanisms as well as through nonpolar Hofmeister effects.In the present work,a continuum solvation based model is developed to explore the impact of salt on pro...Salt influences protein stability through electrostatic mechanisms as well as through nonpolar Hofmeister effects.In the present work,a continuum solvation based model is developed to explore the impact of salt on protein stability.This model relies on a traditional Poisson-Boltzmann(PB)term to describe the polar or electrostatic effects of salt,and a surface area dependent term containing a salt concentration dependent microscopic surface tension function to capture the non-polar Hofmeister effects.The model is first validated against a series of cold-shock protein variants whose salt-dependent protein fold stability profiles have been previously determined experimentally.The approach is then applied to HIV-1 protease in order to explain an experimentally observed enhancement in stability and activity at high(1M)NaCl concentration.The inclusion of the salt-dependent non-polar term brings the model into quantitative agreement with experiment,and provides the basis for further studies into the impact of ionic strength on protein structure,function,and evolution.展开更多
Developing metal-organic framework(MOF)materials with the moisture-resistant feature is highly desirable for CO_(2)capture from highly humid flue gas.In this work,a new core-shell MOF@MOF composite using Mg-MOF-74 wit...Developing metal-organic framework(MOF)materials with the moisture-resistant feature is highly desirable for CO_(2)capture from highly humid flue gas.In this work,a new core-shell MOF@MOF composite using Mg-MOF-74 with high CO_(2)capture capacity as a functional core and hydrophobic zeolitic imidazolate framework-8(ZIF-8)as a protective shell is fabricated by the epitaxial growth method.Experimental results show that the CO_(2)adsorption performance of the core-shell structured Mg-MOF-74@ZIF-8 composites from water-containing flue gas is enhanced along with their improved hydrophobicity.The dynamic breakthrough results show that the Mg-MOF-74@ZIF-8 with three assembled layers(Mg-MOF-74@ZIF-8-3)can capture 3.56 mmol-g^(-1)CO_(2)from wet CO_(2)/N_(2)(VCO_(2):V_(N_(2))=15:85)mixtures,which outperforms Mg-MOF-74(0.37 mmol·g^(-1))and most of the reported physisorbents.展开更多
A new metal-organic framework based on ethyl 1H-tetrazole-5-acetate (Hetza), [Ag4(etza)4] (1), has been synthesized and characterized by elemental analysis, IR, thermal gravimetric and X-ray structural analysis....A new metal-organic framework based on ethyl 1H-tetrazole-5-acetate (Hetza), [Ag4(etza)4] (1), has been synthesized and characterized by elemental analysis, IR, thermal gravimetric and X-ray structural analysis. Crystal data for the title complex are as follows: triclinic system, space group P1 with a = 11.0771(6), b = 11.6636(6), c = 13.2925(8), a = 102.3710(10), β =103.3810(10), γ = 90.0890(10)°, V = 1629.60(16) A3, Mr = 1052.06, Z = 2, F(000) = 1024, Dc = 2.144 g/cm3, μ(MoKa) = 2.438 mm^-1, the final R = 0.0538 and wR = 0.1475 (I 〉 2σ(I)). Complex 1 adopts the (4.82) topological network and the alternately hydrophilic-hydrophilic and hydropho- bic-hydrophobic arrangements. The luminescent properties of complex 1 and the free Hetza ligand have been studied in the solid states.展开更多
The use of trichlorphon in large quantities causes a large number of organic pollutants to enter water, sediments, and soils. Phyllosilicate minerals are considered effective adsorbents for organic pollutants. However...The use of trichlorphon in large quantities causes a large number of organic pollutants to enter water, sediments, and soils. Phyllosilicate minerals are considered effective adsorbents for organic pollutants. However, the adsorption behavior of organic pollutants on soil minerals affected by low-molecular-weight organic acids(LMWOAs) is not fully understood. In this study, the effect of LMWOAs on the adsorption behavior of trichlorphon on phyllosilicate minerals was investigated using a combination of adsorption measurements and molecular spectroscopic techniques(attenuated total reflection-Fourier transform infrared spectroscopy(ATR-FTIR) and X-ray photoelectron spectroscopy(XPS)). The adsorption of trichlorphon onto kaolinite(KAO) and montmorillonite(MON) was suppressed by increasing pH, indicating that electrostatic interaction played a key role in adsorption, especially at low pH. In the presence of citric acid(CA), there was an obvious promotion of trichlorphon adsorption on KAO and MON. In the presence of oxalic acid(OA), the adsorption of trichlorphon on KAO was promoted, whereas the adsorption on MON was inhibited, especially at pH 4.0. The presence of CA and OA increased the adsorption by increasing the exposure of hydrophobic sites of KAO and MON. The results from ATR-FTIR and XPS also indicated that the hydrophobic Si–O sites of phyllosilicate minerals were the preferred adsorption sites for trichlorphon in the presence of CA and OA, probably driven by the hydrophobic effect. However, the weak effect of OA on MON caused an increase in the electrostatic repulsion between MON and trichlorphon molecules, thus inhibiting adsorption. This study is significant for a deeper understanding of self-purification of soil and sediment systems in the presence of organic pollutants.展开更多
Molecular recognition in water,the biological solvent,always receives significant research focus in supramolecular chemistry.The mechanisms of molecular recognition in water is key to comprehending biological processe...Molecular recognition in water,the biological solvent,always receives significant research focus in supramolecular chemistry.The mechanisms of molecular recognition in water is key to comprehending biological processes at the molecular level.Over the past five decades,supramolecular chemists have developed a vast array of synthetic receptors with highly diverse structures and recognition properties.Among them,cyclophanes represent an important family of macrocyclic receptors that have been extensively explored.The aromatic moieties in cyclophanes not only facilitate chemical modifications to impart water solubility but also enable forming hydrophobic cavities for guest inclusion in aqueous environments.Pioneered by Koga et al.,who reported the first inclusion complex of cyclophanes in water and solid state,numerous water-soluble cyclophanes,including derivatives of blue box,calixarenes,resorcinarenes,pillararenes,octopusarenes,biphenarenes,coronarenes,and naphthotubes,etc.,have been synthesized and subjected to investigation of the recognition capabilities in aqueous solutions.This review provides an overview of cyclophane receptors designed to bind organic guests in water.We categorize them into two classes based on the modifications made to their hydrophobic cavities:those with“exo-functionalized hydrophobic cavities”and those with“endo-functionalized hydrophobic cavities”.We introduce their distinctive features and discuss strategies to enhance recognition affinity and selectivity.This review aims to inspire the development of novel synthetic receptors with intriguing properties and foster practical applications of cyclophanes.展开更多
The superhydrophobic strain sensor is a fantastic direction,which could protect the strain sensor in harsh environment.Nevertheless,the self-healing superhydrophobic strain sensor has not been reported.In this researc...The superhydrophobic strain sensor is a fantastic direction,which could protect the strain sensor in harsh environment.Nevertheless,the self-healing superhydrophobic strain sensor has not been reported.In this research,we developed a superhydrophobic strain sensor,which demonstrated excellent self-healing,mechanical robustness,and liquid impalement resistance simultaneously.The key innovation is to partially embed hydrophobic graphene and carbon nanotubes into the hydrogel matrix.The hodrogel substrate endows the sample with self-healing property.The graphene,carbon nanotubes and hydrogel together lead to an accurate and real-time monitoring of human motion.Furthermore,the prepared sample demonstrated super-robust superhydrophobicity,which retained superhydrophobicity after many kinds of damage(such as 1000%stretch,10000 stretching-releasing cycles,hand-rub,tape-peeling,and high-speed drop/jet impact).展开更多
Effects of temperature on self-interaction of human-like collagen (HLC) were investigated by hydrophobic in- teraction chromatography, calorimetric measurement, and sodium dodecyl sulphate-polyacrylamide gel electro...Effects of temperature on self-interaction of human-like collagen (HLC) were investigated by hydrophobic in- teraction chromatography, calorimetric measurement, and sodium dodecyl sulphate-polyacrylamide gel electropho- resis (SDS-PAGE) analysis. Results show that three types of interaction roles may exist between ttLC molecules at 3--50 ℃, which were divided into three narrower temperature ranges. In temperature range from 3--22 ℃, hy- drogen bonding plays a key role in the formation of a gelatinous aggregate. In the range of 22--38 ℃, hydrophobic bonds accompanied by hydrogen bonds are involved in the formation compact aggregates. When temperature is above 38 ℃ the hydrophobic effect formed in the HLC monomer results in the loss of its ability to self-interact.展开更多
In this research,core-shell electrospun fibers loaded with the shell of cellulose acetate and the core of oleic acid and alkyd varnish resin were synthesized and used within poly(dimethyl siloxane)(PDMS)to prepare sel...In this research,core-shell electrospun fibers loaded with the shell of cellulose acetate and the core of oleic acid and alkyd varnish resin were synthesized and used within poly(dimethyl siloxane)(PDMS)to prepare self-healing and p H-responsive coatings for a steel substrate.The morphology of the electrospun fibers was characterized by scanning electron microscopy,transmission electron microscopy and confocal fluorescence microscopy.Thermo gravimetric analysis and Fourier transform infrared spectroscopy revealed that the self-healing agents were loaded successfully with a loading rate of 2.9%.The properties of the fiber-PDMS composite coating were characterized by water contact angle measurements,mechanical tests,electrochemical impedance spectroscopy,and scanning Kelvin probe.Results show that the maximum self-healing efficiencies of the fiber-PDMS coating in alkaline and acidic solution are 95.96%and 97.04%,respectively.The composition of the self-healing agents at the damaged part of the coating was verified by an infrared mapping test and using an energy dispersive spectrometer.In addition,the sandpaper abrasion test shows the hydrophobic effect of fiber-PDMS coating remains above 88.2%and decreases slightly through the addition of abrasion cycles.This research can pave the way for the industrial applications of p H-responsive self-healing coatings.展开更多
The applications of nanotechnology in biomedicine have gained considerable attentions in recent years owing to the great enhancement of therapeutic efficiency.Integration of self-assembly into nanotechnology has broug...The applications of nanotechnology in biomedicine have gained considerable attentions in recent years owing to the great enhancement of therapeutic efficiency.Integration of self-assembly into nanotechnology has brought tremendous convenience during the formation of nano-carriers.Based on distinctive methods of self-assembly,nano-therapeutics have beer~developed to ar~impressive stage with the ability to perform site-specific delivery with temporal and spatial control.This review focuses on the recent advances in the preparing methods for nano-therapeutics,and their applications in the treatments of diseases.展开更多
It is challenging to recognize neutral hydrophilic molecules in water.Effective use of hydrogen bonds in water is generally accepted to be the key to success.In contrast,hydrophobic cavity is usually considered to pla...It is challenging to recognize neutral hydrophilic molecules in water.Effective use of hydrogen bonds in water is generally accepted to be the key to success.In contrast,hydrophobic cavity is usually considered to play an insignificant role or only to provide a nonpolar microenvironment for hydrogen bonds.Herein,we report that hydrophobic cavity alone can also strongly bind neutral,highly hydrophilic molecules in water.We found that cucurbit[n]urils(n=7,8)bind 1,4-dioxane,crown ethers and monosaccharides in water with remarkable affinities.The best binding constant reaches 10^(7) M^(−1) for cucurbit[8]uril,which is higher than its binding affinities to common organic cations.Density functional theory(DFT)calculations and control experiments reveal that the hydrophobic effect is the major contributor to the binding through releasing the cavity water and/or properly occupying the weakly hydrated cavity.However,hydrophobic cavity still prefers nonpolar guests over polar guests with similar size and shape.展开更多
基金This work was supported by the National Natural Science Foundation of China(No.21871063)Guizhou University(No.YJSCXJH(2019)012).
文摘An un precedented tun able hydrophobic effect in self-assembly of a small cationic organic fluorophore(NI-TPy^(+))-based with aggregation-induced emission(AIE)property was realized in aqueous solution.The amplification of hydrophobicity was found to be significantly dependent upon the increasing aggregates of NI-TPy^(+),which enabled the study of the hydrophobic binding of chaotropic anions with the Hofmeister series.
文摘Salt influences protein stability through electrostatic mechanisms as well as through nonpolar Hofmeister effects.In the present work,a continuum solvation based model is developed to explore the impact of salt on protein stability.This model relies on a traditional Poisson-Boltzmann(PB)term to describe the polar or electrostatic effects of salt,and a surface area dependent term containing a salt concentration dependent microscopic surface tension function to capture the non-polar Hofmeister effects.The model is first validated against a series of cold-shock protein variants whose salt-dependent protein fold stability profiles have been previously determined experimentally.The approach is then applied to HIV-1 protease in order to explain an experimentally observed enhancement in stability and activity at high(1M)NaCl concentration.The inclusion of the salt-dependent non-polar term brings the model into quantitative agreement with experiment,and provides the basis for further studies into the impact of ionic strength on protein structure,function,and evolution.
基金supported by the National Natural Science Foundation of China(51772329,51972340,and 51825201)。
文摘Developing metal-organic framework(MOF)materials with the moisture-resistant feature is highly desirable for CO_(2)capture from highly humid flue gas.In this work,a new core-shell MOF@MOF composite using Mg-MOF-74 with high CO_(2)capture capacity as a functional core and hydrophobic zeolitic imidazolate framework-8(ZIF-8)as a protective shell is fabricated by the epitaxial growth method.Experimental results show that the CO_(2)adsorption performance of the core-shell structured Mg-MOF-74@ZIF-8 composites from water-containing flue gas is enhanced along with their improved hydrophobicity.The dynamic breakthrough results show that the Mg-MOF-74@ZIF-8 with three assembled layers(Mg-MOF-74@ZIF-8-3)can capture 3.56 mmol-g^(-1)CO_(2)from wet CO_(2)/N_(2)(VCO_(2):V_(N_(2))=15:85)mixtures,which outperforms Mg-MOF-74(0.37 mmol·g^(-1))and most of the reported physisorbents.
基金supported by National Natural Science Foundation of China(21401147)Basic Research Program of Natural Science from Shaanxi Provincial Government(2015JQ2032)+2 种基金Scientific Research Program from Education Department of Shaanxi Provincial Government(2013JK0654)Opening Foundation from State Key Laboratory of Coordination Chemistry in Nanjing University(201219)and the Program for Distinguished Young Scholars of Xi’an Polythenic University(201403)
文摘A new metal-organic framework based on ethyl 1H-tetrazole-5-acetate (Hetza), [Ag4(etza)4] (1), has been synthesized and characterized by elemental analysis, IR, thermal gravimetric and X-ray structural analysis. Crystal data for the title complex are as follows: triclinic system, space group P1 with a = 11.0771(6), b = 11.6636(6), c = 13.2925(8), a = 102.3710(10), β =103.3810(10), γ = 90.0890(10)°, V = 1629.60(16) A3, Mr = 1052.06, Z = 2, F(000) = 1024, Dc = 2.144 g/cm3, μ(MoKa) = 2.438 mm^-1, the final R = 0.0538 and wR = 0.1475 (I 〉 2σ(I)). Complex 1 adopts the (4.82) topological network and the alternately hydrophilic-hydrophilic and hydropho- bic-hydrophobic arrangements. The luminescent properties of complex 1 and the free Hetza ligand have been studied in the solid states.
基金financially supported by the National Natural Science Foundation of China(Nos.41825021,42007020,and 21876097)the National Natural Science Foundation Project of International Cooperation and Exchange,China(No.41961144010)。
文摘The use of trichlorphon in large quantities causes a large number of organic pollutants to enter water, sediments, and soils. Phyllosilicate minerals are considered effective adsorbents for organic pollutants. However, the adsorption behavior of organic pollutants on soil minerals affected by low-molecular-weight organic acids(LMWOAs) is not fully understood. In this study, the effect of LMWOAs on the adsorption behavior of trichlorphon on phyllosilicate minerals was investigated using a combination of adsorption measurements and molecular spectroscopic techniques(attenuated total reflection-Fourier transform infrared spectroscopy(ATR-FTIR) and X-ray photoelectron spectroscopy(XPS)). The adsorption of trichlorphon onto kaolinite(KAO) and montmorillonite(MON) was suppressed by increasing pH, indicating that electrostatic interaction played a key role in adsorption, especially at low pH. In the presence of citric acid(CA), there was an obvious promotion of trichlorphon adsorption on KAO and MON. In the presence of oxalic acid(OA), the adsorption of trichlorphon on KAO was promoted, whereas the adsorption on MON was inhibited, especially at pH 4.0. The presence of CA and OA increased the adsorption by increasing the exposure of hydrophobic sites of KAO and MON. The results from ATR-FTIR and XPS also indicated that the hydrophobic Si–O sites of phyllosilicate minerals were the preferred adsorption sites for trichlorphon in the presence of CA and OA, probably driven by the hydrophobic effect. However, the weak effect of OA on MON caused an increase in the electrostatic repulsion between MON and trichlorphon molecules, thus inhibiting adsorption. This study is significant for a deeper understanding of self-purification of soil and sediment systems in the presence of organic pollutants.
基金supported by the National Natural Science Foundation of China(Nos.22271164,U20A20259)the Fundamental Research Funds for the Central Universitiesthe NCC Fund(No.NCC2020FH04).
文摘Molecular recognition in water,the biological solvent,always receives significant research focus in supramolecular chemistry.The mechanisms of molecular recognition in water is key to comprehending biological processes at the molecular level.Over the past five decades,supramolecular chemists have developed a vast array of synthetic receptors with highly diverse structures and recognition properties.Among them,cyclophanes represent an important family of macrocyclic receptors that have been extensively explored.The aromatic moieties in cyclophanes not only facilitate chemical modifications to impart water solubility but also enable forming hydrophobic cavities for guest inclusion in aqueous environments.Pioneered by Koga et al.,who reported the first inclusion complex of cyclophanes in water and solid state,numerous water-soluble cyclophanes,including derivatives of blue box,calixarenes,resorcinarenes,pillararenes,octopusarenes,biphenarenes,coronarenes,and naphthotubes,etc.,have been synthesized and subjected to investigation of the recognition capabilities in aqueous solutions.This review provides an overview of cyclophane receptors designed to bind organic guests in water.We categorize them into two classes based on the modifications made to their hydrophobic cavities:those with“exo-functionalized hydrophobic cavities”and those with“endo-functionalized hydrophobic cavities”.We introduce their distinctive features and discuss strategies to enhance recognition affinity and selectivity.This review aims to inspire the development of novel synthetic receptors with intriguing properties and foster practical applications of cyclophanes.
基金This work was supported by the National Natural Science Foundation of China(Nos.51977079,51607067)the Top Young Innovative Talents of Colleges and Universities of Higher Learning Institutions of Hebei(No.BJ2021095)+1 种基金the Youth Elite Scientists Sponsorship Program by Chinese Society for Electrical Engineering(No.CSEE-YESS-2017002)the Fundamental Research Funds for the Central Universities(Nos.2020MS115,2017MS149).
文摘The superhydrophobic strain sensor is a fantastic direction,which could protect the strain sensor in harsh environment.Nevertheless,the self-healing superhydrophobic strain sensor has not been reported.In this research,we developed a superhydrophobic strain sensor,which demonstrated excellent self-healing,mechanical robustness,and liquid impalement resistance simultaneously.The key innovation is to partially embed hydrophobic graphene and carbon nanotubes into the hydrogel matrix.The hodrogel substrate endows the sample with self-healing property.The graphene,carbon nanotubes and hydrogel together lead to an accurate and real-time monitoring of human motion.Furthermore,the prepared sample demonstrated super-robust superhydrophobicity,which retained superhydrophobicity after many kinds of damage(such as 1000%stretch,10000 stretching-releasing cycles,hand-rub,tape-peeling,and high-speed drop/jet impact).
文摘Effects of temperature on self-interaction of human-like collagen (HLC) were investigated by hydrophobic in- teraction chromatography, calorimetric measurement, and sodium dodecyl sulphate-polyacrylamide gel electropho- resis (SDS-PAGE) analysis. Results show that three types of interaction roles may exist between ttLC molecules at 3--50 ℃, which were divided into three narrower temperature ranges. In temperature range from 3--22 ℃, hy- drogen bonding plays a key role in the formation of a gelatinous aggregate. In the range of 22--38 ℃, hydrophobic bonds accompanied by hydrogen bonds are involved in the formation compact aggregates. When temperature is above 38 ℃ the hydrophobic effect formed in the HLC monomer results in the loss of its ability to self-interact.
基金supported by the National Natural Science Foundation of China(Nos.42076039,51801035,51708541,51678318)the Natural Science Foundation of Shandong Province(No.ZR2020ME016)+3 种基金Applied Basic Research Programs of Qingdao[No.E1KY12106N]China Postdoctoral Science Fund[No.2021M693206]the CAS-VPST Silk Road Science Fund 2021(No.133137KYSB20200034)the Natural Science Foundation of Guangxi Province(No.2018GXNSFBA138059)。
文摘In this research,core-shell electrospun fibers loaded with the shell of cellulose acetate and the core of oleic acid and alkyd varnish resin were synthesized and used within poly(dimethyl siloxane)(PDMS)to prepare self-healing and p H-responsive coatings for a steel substrate.The morphology of the electrospun fibers was characterized by scanning electron microscopy,transmission electron microscopy and confocal fluorescence microscopy.Thermo gravimetric analysis and Fourier transform infrared spectroscopy revealed that the self-healing agents were loaded successfully with a loading rate of 2.9%.The properties of the fiber-PDMS composite coating were characterized by water contact angle measurements,mechanical tests,electrochemical impedance spectroscopy,and scanning Kelvin probe.Results show that the maximum self-healing efficiencies of the fiber-PDMS coating in alkaline and acidic solution are 95.96%and 97.04%,respectively.The composition of the self-healing agents at the damaged part of the coating was verified by an infrared mapping test and using an energy dispersive spectrometer.In addition,the sandpaper abrasion test shows the hydrophobic effect of fiber-PDMS coating remains above 88.2%and decreases slightly through the addition of abrasion cycles.This research can pave the way for the industrial applications of p H-responsive self-healing coatings.
基金financially supported by the Thousand Talents Program for Young Professionalsthe National Natural Science Foundation of China(No.51673100)the Fundamental Research Funds for the Central Universities
文摘The applications of nanotechnology in biomedicine have gained considerable attentions in recent years owing to the great enhancement of therapeutic efficiency.Integration of self-assembly into nanotechnology has brought tremendous convenience during the formation of nano-carriers.Based on distinctive methods of self-assembly,nano-therapeutics have beer~developed to ar~impressive stage with the ability to perform site-specific delivery with temporal and spatial control.This review focuses on the recent advances in the preparing methods for nano-therapeutics,and their applications in the treatments of diseases.
基金supported by the National Natural Science Foundation of China(22101125)Shenzhen Science and Technology Innovation Committee(JCYJ20180504165810828)+2 种基金Shenzhen“Pengcheng Scholar”Guangdong High-Level Personnel of Special Support Program(2019TX05C157)Guangdong Provincial Key Laboratory of Catalysis(2020B121201002)。
文摘It is challenging to recognize neutral hydrophilic molecules in water.Effective use of hydrogen bonds in water is generally accepted to be the key to success.In contrast,hydrophobic cavity is usually considered to play an insignificant role or only to provide a nonpolar microenvironment for hydrogen bonds.Herein,we report that hydrophobic cavity alone can also strongly bind neutral,highly hydrophilic molecules in water.We found that cucurbit[n]urils(n=7,8)bind 1,4-dioxane,crown ethers and monosaccharides in water with remarkable affinities.The best binding constant reaches 10^(7) M^(−1) for cucurbit[8]uril,which is higher than its binding affinities to common organic cations.Density functional theory(DFT)calculations and control experiments reveal that the hydrophobic effect is the major contributor to the binding through releasing the cavity water and/or properly occupying the weakly hydrated cavity.However,hydrophobic cavity still prefers nonpolar guests over polar guests with similar size and shape.