Two compounds were isolated from ethyl acetate extract of the fermentation of fungus 07-11, which obtained from the soil of Yunnan Province. They were identified as N-(4-hydroxy-2-methoxyphenyl) acetamide (1) and ergo...Two compounds were isolated from ethyl acetate extract of the fermentation of fungus 07-11, which obtained from the soil of Yunnan Province. They were identified as N-(4-hydroxy-2-methoxyphenyl) acetamide (1) and ergosta-7,22-diene-3,6-dione (2) respectively on the basis of spectral analyses and physical and chemical identifications. Compound 1 was a new natural product. Compound 2 was firstly isolated from its genus. Spectral data of 1 and complete 1H NMR data of 2 were reported for the first time.展开更多
The effect of sulfur compounds (including sulfur, sulfide, sulfite and sulfate), initial concentration of heavy metal and operating conditions on Cd emission in municipal solid waste (MSW) incineration were invest...The effect of sulfur compounds (including sulfur, sulfide, sulfite and sulfate), initial concentration of heavy metal and operating conditions on Cd emission in municipal solid waste (MSW) incineration were investi-gated using a simulated tubular furnace and simulated MSW spiked with Cd. The concentration of Cd was meas-ured by inductively coupled plasma-atomic emission spectrometry (ICP-AES) after digesting the samples including bottom ash, fly ash and flue gas according to related USEPA methods. The results show that S and Na2S tend to in- crease Cd partitioning in bottom ash, whereas Na2SO3 and Na2SO4 tend to reduce Cd partitioning in bottom ash. The effect of sulfur compounds on Cd partitioning in bottom ash was in the sequence of Na2S〉S〉Na2SO3〉 Na2SO4. chemical equilibrium analysis is also performed to determine the effect of sorbents on Cd adsorption. The calculations show that S presents strong affinity for Cd and restrains Cd adsorption by SiO2, whereas when temperature rises to between 830℃ and 1030℃, Cd adsorption efficiency of SiO2 is over 80% and the efficiency of Al2O3 is up to 85%.展开更多
Plants in genus Kadsura,belong to the Schisandraceae family including genus Schisandra and genus Kadsura,revealed folk efficacy and medicinal application in the treatment of rheumatoid arthritis and gastroenteric diso...Plants in genus Kadsura,belong to the Schisandraceae family including genus Schisandra and genus Kadsura,revealed folk efficacy and medicinal application in the treatment of rheumatoid arthritis and gastroenteric disorders for a long history.Previous study indicated that plants from genus Kadsura mainly contain lignans,triterpenoids and essential oils,and showed the active compounds were lignans and triterpenoids.Among all compounds from Schisandraceae family,the triterpenoids between the genus Schisandra and genus Kadsura had obvious differences.In this paper,we reviewed214triterpenoids and their pharmacological activities reported from genus Kadsura in the past30years(from1987to2017),aiming to provide reference for further study.展开更多
Water oxidation is one of the most important reactions in natural and artificial energy conversion schemes.In nature,solar energy is converted to chemical energy via water oxidation at the oxygen-evolving center of ph...Water oxidation is one of the most important reactions in natural and artificial energy conversion schemes.In nature,solar energy is converted to chemical energy via water oxidation at the oxygen-evolving center of photosystem II to generate dioxygen,protons,and electrons.In artificial energy schemes,water oxidation is one of the half reactions of water splitting,which is an appealing strategy for energy conversion via photocatalytic,electrocatalytic,or photoelectrocatalytic processes.Because it is thermodynamically unfavorable and kinetically slow,water oxidation is the bottleneck for achieving large-scale water splitting.Thus,developing highly efficient water oxidation catalysts has attracted the interests of researchers in the past decades.The formation of O-O bonds is typically the rate-determining step of the water oxidation catalytic cycle.Therefore,better understanding this key step is critical for the rational design of more efficient catalysts.This review focuses on elucidating the evolution of metal-oxygen species during transition metal-catalyzed water oxidation,and more importantly,on discussing the feasible O-O bond formation mechanisms during the oxygen evolution reaction over synthetic molecular catalysts.展开更多
The laser-induced fluorescence excitation spectrum of CoC was recorded in the spectral region from 13500 cm^-1 to 22000 cm^-1, in which the CoC molecules were produced by the reaction of sputtered cobalt atoms with me...The laser-induced fluorescence excitation spectrum of CoC was recorded in the spectral region from 13500 cm^-1 to 22000 cm^-1, in which the CoC molecules were produced by the reaction of sputtered cobalt atoms with methanol under supersonic jet cooled conditions. Much of the visible spectrum was assigned to transitions between the X2∑^+ ground state and F2∑^+ state. The 11 bands assigned as (v'=3-13, 0) transitions of the F^2∑^+-X^2∑^+ band system were observed and rotationally analyzed. Equilibrium constants for the F^2∑^+ state were Te=13628 cm^-1, We=669 cm^-1, ωeХe=4.3 cm^-1, Be=0.546 cm^-1, and Re=1.758A. Some new bands were observed.展开更多
The aromaticity of all possible substituted fullerene isomers of C18N2, C18B2, C18BN, and their molecular ions which originate from the C20 (Ih) cage were studied by the topological resonance energy (TRE) and the ...The aromaticity of all possible substituted fullerene isomers of C18N2, C18B2, C18BN, and their molecular ions which originate from the C20 (Ih) cage were studied by the topological resonance energy (TRE) and the percentage topological resonance energy methods. The relationship between the aromaticity of C18BxNy isomers and the sites where the heteroatoms dope at the C20 (Ih) cage is discussed. Calculation results show that at the neutral and cationic states all the isomers are predicted to be antiaromatic with negative TREs, but their polyvalent anions are predicted to be aromatic with positive TREs. The most stable isomer is formed by heteroatom doping at the 1,11-sites in C18N2. C18B2, and C18BN. Heterofullerenes are more aromatic than C20. The stability order in the neutral states is C18N2〉C18BN〉C18B2〉C20. The stability order in closed-shell is C18B2^8- 〉C20^6- 〉C18BN^6- 〉C18N2^4-. This predicts theoretically that their polyvalent anions have high aromaticity.展开更多
Ti0.5Al0.25Ni0.25 alloy prepared by vacuum induction melting was studied.The phase composition was analyzed with X-ray technique and EDS analysis,and its electrochemical properties were investigated at various tempera...Ti0.5Al0.25Ni0.25 alloy prepared by vacuum induction melting was studied.The phase composition was analyzed with X-ray technique and EDS analysis,and its electrochemical properties were investigated at various temperatures.Electrochemical reaction kinetic parameters were also studied with proper electrochemical techniques.The influence of the secondary corrosion reaction on the anodic linear polarization measurement was also analyzed by theoretical simulation.The results show that,proper ball-milling with nickel powders is beneficial to electrochemical performance.The theoretical simulation proves that,the existence of the side reaction can disturb the measurement of electrochemical reaction kinetic parameters.展开更多
The value of social security funds, has always been an important part of our country social security enterprise as a whole, it is the one of the main ways to realize the social stability and national economic income. ...The value of social security funds, has always been an important part of our country social security enterprise as a whole, it is the one of the main ways to realize the social stability and national economic income. In the triple pressure with ageing population, inflation and social security transition, the value of the social security fund in our country is particularly acute. Analyses the receipts and expenditures of social security funds, investment and operation structure and put forward some rationalization proposal, which has significant meaning for a better play to the role of the social security fund and actively promote the innovation and development of China's social security fund management.展开更多
This paper presents a new online incremental training algorithm of Gaussian mixture model (GMM), which aims to perform the expectation-maximization(EM) training incrementally to update GMM model parameters online ...This paper presents a new online incremental training algorithm of Gaussian mixture model (GMM), which aims to perform the expectation-maximization(EM) training incrementally to update GMM model parameters online sample by sample, instead of waiting for a block of data with the sufficient size to start training as in the traditional EM procedure. The proposed method is extended from the split-and-merge EM procedure, so inherently it is also capable escaping from local maxima and reducing the chances of singularities. In the application domain, the algorithm is optimized in the context of speech processing applications. Experiments on the synthetic data show the advantage and efficiency of the new method and the results in a speech processing task also confirm the improvement of system performance.展开更多
This work aims to show, in the phenomenology of Husserl, the relevance to seek the elements that give epistemological legitimacy and validity to the conceptualization that brings psychoanalytic theory to account for p...This work aims to show, in the phenomenology of Husserl, the relevance to seek the elements that give epistemological legitimacy and validity to the conceptualization that brings psychoanalytic theory to account for processes whose explanation necessarily imply to clarify that psychoanalysis, in contrast to psychological treatments, is not based on the effects of a relationship between the participants but in the positioning that each of them occupies relative to the other, particularly when having in mind the concept of transference and recognizing in it the position from which the analyst can give conditions of possibility--through his interventions--for which the patient may realize, analyze, and rethink his own position on what constitutes his discomfort. Husserl recaptures the Cartesian base from which opens philosophical reflection to a new area of research "in" consciousness where it is allowed to understand the relationship between subject and object from a new perspective that enables establishing an epistemology that substantiates the rigorous analysis of human subjectivity. Husserl's proposal introduces us to an epistemic field in which it can be shown and, that the psychoanalytic method which enables its effects is precisely the position of the analyst, while by his presence and intervention leads to the other in question, without having to abide by an alien desire, be able to position himself before his own desire. This analysis regarding the desire of oneself is indispensable to understand the elements at play in contemporary psychopathology, as in the present context the intensity of the demands generated in the economic apparatus, are experienced by the subject as arising from himself, erasing traces of his desire that is superseded by social imperatives that crushed and fragmented him.展开更多
In the present work, three medium softening point coal tar pitches were used for comparative thermal stability and under-storage stability investigation. Powders of the pitches were found to be different under storage...In the present work, three medium softening point coal tar pitches were used for comparative thermal stability and under-storage stability investigation. Powders of the pitches were found to be different under storage: one of the pitches was caked and slumped after 7-day or longer storage. For thermal stability investigation the soft temperature treatment (265℃) of coal tar pitches was used. Detailed study of initial and treated pitches was carried out. Experimental results demonstrated that LMW-HC (high low-molecular-weight hydrocarbons) and oxygen content influence pitch quality characteristics in a negative way under long-term storage and lead to highest properties change after thermal stability treatment.展开更多
This paper describes the fabrication, characterization and properties of a novel hybrid poly(ethylene glycol) (PEG) based hydrogel via in situ polymerization. The hybrid hydrogel was fabricated by free-radical red...This paper describes the fabrication, characterization and properties of a novel hybrid poly(ethylene glycol) (PEG) based hydrogel via in situ polymerization. The hybrid hydrogel was fabricated by free-radical redox polymerization using ammonium persulfate (APS) and N, N, N/, NCtetramethylethylenediamine (TEMED) as initiators and N, NCmethylene bisacrylamide (BIS) as cross-linker at 60~C. To create a hybrid hydrogel, 0.2% (mass fraction) of MgA1 layered double hydroxide (LDH) was added to the aqueous solution by ultrasonic disper- sion. The physicochemical properties of hybrid hydrogel under vacuum freeze-drying processing were characterized by Fourier transform infrared (FTIR) spectroscopy, thermal gravimetric analysis (TGA) and scanning electron microscopy (SEM), while swelling kinetics and gel content were calculated. Swelling degree in distilled water varied from 94%--125% with a gel mass fraction of 83%--91%. SEM images showed that the micron pore size of hydrogel could be adjusted within the range of several micrometers by changing the cross-linker mass fraction from 2% to 10% (based on glycol). The results showed that the hybrid hydrogels exhibited excellent physicochemical behavior and might be a promising material for applications in tissue engineering and drug delivery.展开更多
The thermal conductivity of methane hydrate is an important physical parameter affecting the processes of methane hydrate exploration,mining,gas hydrate storage and transportation as well as other applications.Equilib...The thermal conductivity of methane hydrate is an important physical parameter affecting the processes of methane hydrate exploration,mining,gas hydrate storage and transportation as well as other applications.Equilibrium molecular dynamics simulations and the Green-Kubo method have been employed for systems from fully occupied to vacant occupied sI methane hydrate in order to estimate their thermal conductivity.The estimations were carried out at temperatures from 203.15 to 263.15 K and at pressures from 3 to 100 MPa.Potential models selected for water were TIP4P,TIP4P-Ew,TIP4P/2005,TIP4P-FQ and TIP4P/Ice.The effects of varying the ratio of the host and guest molecules and the external thermobaric conditions on the thermal conductivity of methane hydrate were studied.The results indicated that the thermal conductivity of methane hydrate is essentially determined by the cage framework which constitutes the hydrate lattice and the cage framework has only slightly higher thermal conductivity in the presence of the guest molecules.Inclusion of more guest molecules in the cage improves the thermal conductivity of methane hydrate.It is also revealed that the thermal conductivity of the sI hydrate shows a similar variation with temperature.Pressure also has an effect on the thermal conductivity,particularly at higher pressures.As the pressure increases,slightly higher thermal conductivities result.Changes in density have little impact on the thermal conductivity of methane hydrate.展开更多
The mechanism of the action of copper-dependent quercetin 2,3-dioxygenase (2,3QD) has been investigated by means of hy- brid density functional theory. The 2,3QD enzyme cleaves the O-heterocycle of a quercetin by in...The mechanism of the action of copper-dependent quercetin 2,3-dioxygenase (2,3QD) has been investigated by means of hy- brid density functional theory. The 2,3QD enzyme cleaves the O-heterocycle of a quercetin by incorporation of both oxygen atoms into the substrate and releases carbon monoxide. The calculations show that dioxygen attack on the copper complex is energetically favorable. The adduct has a possible near-degeneracy of states between [Cu2+-(substrate H+)] and [Cu+-(sub- strate-H). ], and in addition the pyramidalized C2 atom is ideally suited for forming a dioxygembridged structure. In the next step, the C3-C4 bond is cleaved and intermediate lnt5 is formed via transition state TS4. Finally, the Oa-Ob and C2-C3 bonds are cleaved, and CO is released in one concerted transition state (TS5) with the barrier of 63.25 and 61.91 k J/tool in the gas phase and protein environments, respectively. On the basis of our proposed reaction mechanism, this is the rate-limiting step of the whole catalytic cycle and is strongly driven by a relatively large exothermicity of 100.86 kJ/mol. Our work provides some valuable fundamental insights into the behavior of this enzyme.展开更多
基金The present work was supported by Foundation of State Key Basic Research and Development Project (G1998051100)
文摘Two compounds were isolated from ethyl acetate extract of the fermentation of fungus 07-11, which obtained from the soil of Yunnan Province. They were identified as N-(4-hydroxy-2-methoxyphenyl) acetamide (1) and ergosta-7,22-diene-3,6-dione (2) respectively on the basis of spectral analyses and physical and chemical identifications. Compound 1 was a new natural product. Compound 2 was firstly isolated from its genus. Spectral data of 1 and complete 1H NMR data of 2 were reported for the first time.
文摘The effect of sulfur compounds (including sulfur, sulfide, sulfite and sulfate), initial concentration of heavy metal and operating conditions on Cd emission in municipal solid waste (MSW) incineration were investi-gated using a simulated tubular furnace and simulated MSW spiked with Cd. The concentration of Cd was meas-ured by inductively coupled plasma-atomic emission spectrometry (ICP-AES) after digesting the samples including bottom ash, fly ash and flue gas according to related USEPA methods. The results show that S and Na2S tend to in- crease Cd partitioning in bottom ash, whereas Na2SO3 and Na2SO4 tend to reduce Cd partitioning in bottom ash. The effect of sulfur compounds on Cd partitioning in bottom ash was in the sequence of Na2S〉S〉Na2SO3〉 Na2SO4. chemical equilibrium analysis is also performed to determine the effect of sorbents on Cd adsorption. The calculations show that S presents strong affinity for Cd and restrains Cd adsorption by SiO2, whereas when temperature rises to between 830℃ and 1030℃, Cd adsorption efficiency of SiO2 is over 80% and the efficiency of Al2O3 is up to 85%.
基金funding support from Hunan Province Universities 2011 Collaborative Innovation Center of Protection and Utilization of Huxiang Chinese Medicine Resources, Hunan Provincial Key Laboratory of Diagnostics in Chinese Medicine, and National Natural Science Foundation of China (No. 81673579)
文摘Plants in genus Kadsura,belong to the Schisandraceae family including genus Schisandra and genus Kadsura,revealed folk efficacy and medicinal application in the treatment of rheumatoid arthritis and gastroenteric disorders for a long history.Previous study indicated that plants from genus Kadsura mainly contain lignans,triterpenoids and essential oils,and showed the active compounds were lignans and triterpenoids.Among all compounds from Schisandraceae family,the triterpenoids between the genus Schisandra and genus Kadsura had obvious differences.In this paper,we reviewed214triterpenoids and their pharmacological activities reported from genus Kadsura in the past30years(from1987to2017),aiming to provide reference for further study.
文摘Water oxidation is one of the most important reactions in natural and artificial energy conversion schemes.In nature,solar energy is converted to chemical energy via water oxidation at the oxygen-evolving center of photosystem II to generate dioxygen,protons,and electrons.In artificial energy schemes,water oxidation is one of the half reactions of water splitting,which is an appealing strategy for energy conversion via photocatalytic,electrocatalytic,or photoelectrocatalytic processes.Because it is thermodynamically unfavorable and kinetically slow,water oxidation is the bottleneck for achieving large-scale water splitting.Thus,developing highly efficient water oxidation catalysts has attracted the interests of researchers in the past decades.The formation of O-O bonds is typically the rate-determining step of the water oxidation catalytic cycle.Therefore,better understanding this key step is critical for the rational design of more efficient catalysts.This review focuses on elucidating the evolution of metal-oxygen species during transition metal-catalyzed water oxidation,and more importantly,on discussing the feasible O-O bond formation mechanisms during the oxygen evolution reaction over synthetic molecular catalysts.
基金ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (No.20433080 and No.20673107), the National Key Basic Research Special Foundation of China (No.2007CB815203), and the Chinese Academy of Science (KJCX2-YW-N24).
文摘The laser-induced fluorescence excitation spectrum of CoC was recorded in the spectral region from 13500 cm^-1 to 22000 cm^-1, in which the CoC molecules were produced by the reaction of sputtered cobalt atoms with methanol under supersonic jet cooled conditions. Much of the visible spectrum was assigned to transitions between the X2∑^+ ground state and F2∑^+ state. The 11 bands assigned as (v'=3-13, 0) transitions of the F^2∑^+-X^2∑^+ band system were observed and rotationally analyzed. Equilibrium constants for the F^2∑^+ state were Te=13628 cm^-1, We=669 cm^-1, ωeХe=4.3 cm^-1, Be=0.546 cm^-1, and Re=1.758A. Some new bands were observed.
文摘The aromaticity of all possible substituted fullerene isomers of C18N2, C18B2, C18BN, and their molecular ions which originate from the C20 (Ih) cage were studied by the topological resonance energy (TRE) and the percentage topological resonance energy methods. The relationship between the aromaticity of C18BxNy isomers and the sites where the heteroatoms dope at the C20 (Ih) cage is discussed. Calculation results show that at the neutral and cationic states all the isomers are predicted to be antiaromatic with negative TREs, but their polyvalent anions are predicted to be aromatic with positive TREs. The most stable isomer is formed by heteroatom doping at the 1,11-sites in C18N2. C18B2, and C18BN. Heterofullerenes are more aromatic than C20. The stability order in the neutral states is C18N2〉C18BN〉C18B2〉C20. The stability order in closed-shell is C18B2^8- 〉C20^6- 〉C18BN^6- 〉C18N2^4-. This predicts theoretically that their polyvalent anions have high aromaticity.
文摘Ti0.5Al0.25Ni0.25 alloy prepared by vacuum induction melting was studied.The phase composition was analyzed with X-ray technique and EDS analysis,and its electrochemical properties were investigated at various temperatures.Electrochemical reaction kinetic parameters were also studied with proper electrochemical techniques.The influence of the secondary corrosion reaction on the anodic linear polarization measurement was also analyzed by theoretical simulation.The results show that,proper ball-milling with nickel powders is beneficial to electrochemical performance.The theoretical simulation proves that,the existence of the side reaction can disturb the measurement of electrochemical reaction kinetic parameters.
文摘The value of social security funds, has always been an important part of our country social security enterprise as a whole, it is the one of the main ways to realize the social stability and national economic income. In the triple pressure with ageing population, inflation and social security transition, the value of the social security fund in our country is particularly acute. Analyses the receipts and expenditures of social security funds, investment and operation structure and put forward some rationalization proposal, which has significant meaning for a better play to the role of the social security fund and actively promote the innovation and development of China's social security fund management.
文摘This paper presents a new online incremental training algorithm of Gaussian mixture model (GMM), which aims to perform the expectation-maximization(EM) training incrementally to update GMM model parameters online sample by sample, instead of waiting for a block of data with the sufficient size to start training as in the traditional EM procedure. The proposed method is extended from the split-and-merge EM procedure, so inherently it is also capable escaping from local maxima and reducing the chances of singularities. In the application domain, the algorithm is optimized in the context of speech processing applications. Experiments on the synthetic data show the advantage and efficiency of the new method and the results in a speech processing task also confirm the improvement of system performance.
文摘This work aims to show, in the phenomenology of Husserl, the relevance to seek the elements that give epistemological legitimacy and validity to the conceptualization that brings psychoanalytic theory to account for processes whose explanation necessarily imply to clarify that psychoanalysis, in contrast to psychological treatments, is not based on the effects of a relationship between the participants but in the positioning that each of them occupies relative to the other, particularly when having in mind the concept of transference and recognizing in it the position from which the analyst can give conditions of possibility--through his interventions--for which the patient may realize, analyze, and rethink his own position on what constitutes his discomfort. Husserl recaptures the Cartesian base from which opens philosophical reflection to a new area of research "in" consciousness where it is allowed to understand the relationship between subject and object from a new perspective that enables establishing an epistemology that substantiates the rigorous analysis of human subjectivity. Husserl's proposal introduces us to an epistemic field in which it can be shown and, that the psychoanalytic method which enables its effects is precisely the position of the analyst, while by his presence and intervention leads to the other in question, without having to abide by an alien desire, be able to position himself before his own desire. This analysis regarding the desire of oneself is indispensable to understand the elements at play in contemporary psychopathology, as in the present context the intensity of the demands generated in the economic apparatus, are experienced by the subject as arising from himself, erasing traces of his desire that is superseded by social imperatives that crushed and fragmented him.
文摘In the present work, three medium softening point coal tar pitches were used for comparative thermal stability and under-storage stability investigation. Powders of the pitches were found to be different under storage: one of the pitches was caked and slumped after 7-day or longer storage. For thermal stability investigation the soft temperature treatment (265℃) of coal tar pitches was used. Detailed study of initial and treated pitches was carried out. Experimental results demonstrated that LMW-HC (high low-molecular-weight hydrocarbons) and oxygen content influence pitch quality characteristics in a negative way under long-term storage and lead to highest properties change after thermal stability treatment.
基金the National Natural Science Foundation of China(No.31000427)the China Postdoctoral Science Foundation(No.20100481214)the Fundamental Research Funds for the Central Universities of China(Nos.2012QN052 and 2012TD013)
文摘This paper describes the fabrication, characterization and properties of a novel hybrid poly(ethylene glycol) (PEG) based hydrogel via in situ polymerization. The hybrid hydrogel was fabricated by free-radical redox polymerization using ammonium persulfate (APS) and N, N, N/, NCtetramethylethylenediamine (TEMED) as initiators and N, NCmethylene bisacrylamide (BIS) as cross-linker at 60~C. To create a hybrid hydrogel, 0.2% (mass fraction) of MgA1 layered double hydroxide (LDH) was added to the aqueous solution by ultrasonic disper- sion. The physicochemical properties of hybrid hydrogel under vacuum freeze-drying processing were characterized by Fourier transform infrared (FTIR) spectroscopy, thermal gravimetric analysis (TGA) and scanning electron microscopy (SEM), while swelling kinetics and gel content were calculated. Swelling degree in distilled water varied from 94%--125% with a gel mass fraction of 83%--91%. SEM images showed that the micron pore size of hydrogel could be adjusted within the range of several micrometers by changing the cross-linker mass fraction from 2% to 10% (based on glycol). The results showed that the hybrid hydrogels exhibited excellent physicochemical behavior and might be a promising material for applications in tissue engineering and drug delivery.
基金supported by the National Natural Science Foundation of China(51106163)the National Basic Research Program of China (2009CB219504)the Joint Funds of NSFC with the Government of Guangdong Province(U0933004)
文摘The thermal conductivity of methane hydrate is an important physical parameter affecting the processes of methane hydrate exploration,mining,gas hydrate storage and transportation as well as other applications.Equilibrium molecular dynamics simulations and the Green-Kubo method have been employed for systems from fully occupied to vacant occupied sI methane hydrate in order to estimate their thermal conductivity.The estimations were carried out at temperatures from 203.15 to 263.15 K and at pressures from 3 to 100 MPa.Potential models selected for water were TIP4P,TIP4P-Ew,TIP4P/2005,TIP4P-FQ and TIP4P/Ice.The effects of varying the ratio of the host and guest molecules and the external thermobaric conditions on the thermal conductivity of methane hydrate were studied.The results indicated that the thermal conductivity of methane hydrate is essentially determined by the cage framework which constitutes the hydrate lattice and the cage framework has only slightly higher thermal conductivity in the presence of the guest molecules.Inclusion of more guest molecules in the cage improves the thermal conductivity of methane hydrate.It is also revealed that the thermal conductivity of the sI hydrate shows a similar variation with temperature.Pressure also has an effect on the thermal conductivity,particularly at higher pressures.As the pressure increases,slightly higher thermal conductivities result.Changes in density have little impact on the thermal conductivity of methane hydrate.
基金supported by the National Natural Science Foundation of China (21073164,20673098)the Natural Science Foundation of Zhejiang Province (Y4100620)the Research Foundation of the Education Bureau of Zhejiang Province (Y200906517)
文摘The mechanism of the action of copper-dependent quercetin 2,3-dioxygenase (2,3QD) has been investigated by means of hy- brid density functional theory. The 2,3QD enzyme cleaves the O-heterocycle of a quercetin by incorporation of both oxygen atoms into the substrate and releases carbon monoxide. The calculations show that dioxygen attack on the copper complex is energetically favorable. The adduct has a possible near-degeneracy of states between [Cu2+-(substrate H+)] and [Cu+-(sub- strate-H). ], and in addition the pyramidalized C2 atom is ideally suited for forming a dioxygembridged structure. In the next step, the C3-C4 bond is cleaved and intermediate lnt5 is formed via transition state TS4. Finally, the Oa-Ob and C2-C3 bonds are cleaved, and CO is released in one concerted transition state (TS5) with the barrier of 63.25 and 61.91 k J/tool in the gas phase and protein environments, respectively. On the basis of our proposed reaction mechanism, this is the rate-limiting step of the whole catalytic cycle and is strongly driven by a relatively large exothermicity of 100.86 kJ/mol. Our work provides some valuable fundamental insights into the behavior of this enzyme.