Three Keggin-type heteropolyanions, namely H3PMo12O40-13H2O, （NH4）3PMo12O40·4H2O and H3PW12O40·13H2O were prepared and tested in the ring-opening polymerization reaction of tetrahydrofuran. The effects of ...Three Keggin-type heteropolyanions, namely H3PMo12O40-13H2O, （NH4）3PMo12O40·4H2O and H3PW12O40·13H2O were prepared and tested in the ring-opening polymerization reaction of tetrahydrofuran. The effects of the counter-cation （H＋, NH4＋） and the peripheral atoms （Mo, W） on the polymerization were investigated. It has been found that when the protons of H3PMo12O40·13H2O were replaced by the ammonium cations the polymerization rate decreased dramatically. Whereas, when the peripheral atoms （Mo） were replaced by their homologous （W）, the polymerization rate increased twofold. As for the viscosity average molecular weight （My） of polymer products, it was found that the high molecular weight （7930） was obtained by using H3PW12O40·13H2O. The molecular weight （My） obtained by H3PMo12O40·13H2O and （NH4）H3PMo12O40·13H2O was 6470 and 6810, respectively.展开更多
Two photochromic compounds with the pyrazolonering as the photochromic functional structure, 2(1phenyl3methyl4benzoformylpyrazolone5)thiosemicarbazone(PMBPTSC) and 2(1phenyl3methyl4benzoformylpyrazolone5)smethylthiose...Two photochromic compounds with the pyrazolonering as the photochromic functional structure, 2(1phenyl3methyl4benzoformylpyrazolone5)thiosemicarbazone(PMBPTSC) and 2(1phenyl3methyl4benzoformylpyrazolone5)smethylthiosemicarbazone(PMBPMTSC), were synthesized and characterized by elemental analysis, MS, IR spectra, NMR spectra. The crystal structure of the photocolored product of PMBPTSC was determined by single crystal XRD analysis. The results show that the photochromic phenomenon is due to the photoisomerization from enol form to keto form. Their photochromic properties were studied by powderUV reflectance spectra under the irradiation of 200—380 nm light. The firstorder rate constants of the photocoloring reaction were found to be 780×10 -3 s -1 for compound 1A and 103×10 -3 s -1 for compound 2A.展开更多
The reaction of cis- 2- chloro- 4- phenyl- 5, 5- dimethyl- 1, 3. 2-dioxaghosghor inan-2- thione (Ⅰ) with methoxide or phenoxide at room temperatute takes place with retent ion of configuration. while refluxing cis- ...The reaction of cis- 2- chloro- 4- phenyl- 5, 5- dimethyl- 1, 3. 2-dioxaghosghor inan-2- thione (Ⅰ) with methoxide or phenoxide at room temperatute takes place with retent ion of configuration. while refluxing cis- (1) and methoxide in methanol, gartial isomerization of cis-thioghosphate (2) to its trans isomer occursand an acyclic intermediate (3) is found to be involved in this grocess展开更多
Sodium molybdate was reduced to produce ring-like compounds in the presence of carboxylic acids. Compound 1: Na8(H2O)28(H3O)+{Na(DMSO)2[MoVI10MoV8O52(OH)4(CH3C- OO)2]}11H2O (C8H103O102Na9S2Mo18, Mr = 3829.85), where ...Sodium molybdate was reduced to produce ring-like compounds in the presence of carboxylic acids. Compound 1: Na8(H2O)28(H3O)+{Na(DMSO)2[MoVI10MoV8O52(OH)4(CH3C- OO)2]}11H2O (C8H103O102Na9S2Mo18, Mr = 3829.85), where the {Mo18} ring is built up by two acetic acids connecting two {Mo9} building blocks and the 1-D chain of 1 is formed through the coordinated sodium cations. Crystal data: triclinic, space group P, a = 11.3228(2), b = 15.4170(2), c = 16.7209(3) ? a = 113.006(1), b = 108.455(1), g = 92.430(1), V = 2501.98(7) 3, Z = 1, Dc = 2.542 g/cm3, F(000) = 1854, (MoKa) = 2.381 mm-1, T = 293(2) K, final R = 0.0532 and wR = 0.1203 for 7291 observed reflections with I > 2(I) from 8775 independent reflections. Compound 2: Na8(H2O)22(H3O)+{Na(DMSO)2[MoVI10MoV8O52(OH)4(C2H5COO)2]}10H2O (C10H93O94Na9- S2Mo18, Mr = 3715.79). Crystal data: monoclinic, space group C2/m, a = 18.044(1), b = 25.944(2), c = 10.4087(6) ? b = 106.613(2), V = 4669.3(5) 3, Z = 2, Dc = 2.643 g/cm3, F(000) = 3584, (MoKa) = 2.542 mm-1, T = 293(2) K, final R = 0.0536 and wR = 0.1621 for 4617 observed reflections with I > 2(I) from 5398 independent reflections. Similar to 1, the {Mo18} ring is built up by two {Mo9} building blocks that are connected up by two propanoic acids and these {Mo18} rings are further linked into a two-dimensional layer through the coordinated sodium cations.展开更多
The H2Ge=Ge：, as well as and its derivatives （X2Ge=Ge：, X=H, Me, F, C1, Br, Ph, At, ...） is a kind of new species. Its cycloaddition reactions is a new area for the study of germylene chemistry. The mechanism of t...The H2Ge=Ge：, as well as and its derivatives （X2Ge=Ge：, X=H, Me, F, C1, Br, Ph, At, ...） is a kind of new species. Its cycloaddition reactions is a new area for the study of germylene chemistry. The mechanism of the cycloaddition reaction between singlet Me2Ge=Ge： and acetaldehyde was investigated with the B3LYP/6-31G＊ method in this work. From the potential energy profile, it could be predicted that the reaction has one dominant reaction pathway. The reaction rule is that the two reactants firstly form a four-membered Ge-heterocyclic ring germylene through the [2＋2] cycloaddition reaction. Because of the 4p unoccupied orbital of Ge： atom in the four-membered Ge-heterocyclic ring germylene and the ~ orbital of acetaldehyde forming a r^--~p donor-acceptor bond, the four-membered Ge-heterocyclic ring germylene further combines with acetaldehyde to form an intermedi- ate. Because the Ge atom in intermediate happens sp3 hybridization after transition state, then, intermediate isomerizes to a spiro-Ge-heterocyclic ring compound via a transition state. The research result indicates the laws of cycloaddition reaction between Me2Ge=Ge： and ac- etaldehyde, and lays the theory foundation of the cycloaddition reaction between H2Ge=Ge： and its derivatives （X2Ge=Ge：, X=H, Me, F, C1, Br, Ph, At, ...） and asymmetric ^-bonded compounds, which are significant for the synthesis of small-ring and spiro-Ge-heterocyclic ring compounds.展开更多
H2Ge=Si： and its derivatives （X2Ge=Si：, X=H, Me, F, C1, Br, Ph, Ar, ...） are new species. Its cycloaddition reactions are new area for the study of silylene chemistry. The cycloaddition reaction mechanism of singl...H2Ge=Si： and its derivatives （X2Ge=Si：, X=H, Me, F, C1, Br, Ph, Ar, ...） are new species. Its cycloaddition reactions are new area for the study of silylene chemistry. The cycloaddition reaction mechanism of singlet H2Ge=Si： and formaldehyde has been investigated with the MP2/aug-cc-pVDZ method. From the potential energy profile, it could be predicted that the reaction has one dominant reaction pathway. The reaction rule is that two reactants firstly form a four-membered Ge-heterocyclic ring silylene through the [2＋2] cycloaddition reaction. Because of the 3p unoccupied orbital of Si： atom in the four-membered Ge-heterocyclic ring silylene and the π orbital of formaldehyde forming a π--p donor-acceptor bond, the four-membered Ge-heterocyclic ring silylene further combines with formaldehyde to form an intermediate. Because the Si： atom in the intermediate undergoes sp3 hybridization after transition state, then the intermediate isomerizes to a spiro-Si-heterocyclic ring compound involving Ge via a transition state. The result indicates the laws of cycloaddition reaction between H2Ge=Si： or its derivatives （X2Ge=Si：, X=H, Me, F, Cl, Br, Ph, Ar, ...） and asymmetric π-bonded compounds are significant for the synthesis of small-ring involving Si and Ge and spiro-Si-heterocyclic ring compounds involving Ge.展开更多
Characteristics of atmospheric VOCs(volatile organic compounds) have been extensively studied in megacities in China, however, they are scarcely investigated in medium/smallsized cities in North China Plain(NCP).A com...Characteristics of atmospheric VOCs(volatile organic compounds) have been extensively studied in megacities in China, however, they are scarcely investigated in medium/smallsized cities in North China Plain(NCP).A comprehensive research on possible sources of VOCs was conducted in a medium-sized city of NCP, from May to September 2019.A total of 143 canister samples of 8 sites in Xuchang city were collected, and 57 VOC species were detected.The average VOC concentrations were 42.6 ± 31.6 μg/m3, with 53.7 ± 31.0 μg/m3 and 32.1 ± 27.8 μg/m^(3), in the morning and afternoon, respectively.Alkenes and aromatics contributed 80% of the total ozone formation potential(OFP).Aromatics accounted for more than 95% of secondary organic aerosol potential(SOAP).VOCs were dominated by the local emission with significant transport from the southeast direction.PMF analysis extracted 6 sources, which were combustion(33.1%), LPG usage(19.3%), vehicular exhaust & fuel evaporation(15.8%), solvent usage(15.2%), industrial(9.11%) and biogenic(7.51%), respectively and they contributed 33.4%, 17.6%, 12.9%, 18.6%, 9.28% and 8.22% to the OFP, respectively.Combustion and LPG usage were the dominant VOC sources;and combustion, solvent usage and LPG usage were the main sources of OFP in Xuchang city, which were different to megacities in China with a high contribution from vehicular exhaust, solvent usage and industry,suggesting specific control strategies on VOCs need to be implemented in medium-sized city such as Xuchang city.展开更多
The X2Ge=Si： （X = H, Me, F, reaction is a new area for the study of silylene between singlet CI2Ge=Si： and formaldehyde CI, Br, Ph, At...） is a new species. Its cycloaddition chemistry. The mechanism of cycloaddit...The X2Ge=Si： （X = H, Me, F, reaction is a new area for the study of silylene between singlet CI2Ge=Si： and formaldehyde CI, Br, Ph, At...） is a new species. Its cycloaddition chemistry. The mechanism of cycloaddition reaction has been investigated with CCSD（T）//MP2/6-31G＊ method. From the potential energy profile, it can be predicted that the reaction has two competitive dominant reaction pathways. The reaction rule presented is that the two reactants firstly form a four-membered Ge-heterocyclic ring silylene through the [2＋2] cycloaddition reaction. Owing to the 3p unoccupied orbital of Si： atom in the four-membered Ge-heterocyclic ring silylene and the π orbital of formaldehyde forming a π-p donor-acceptor bond, the four-membered Ge-heterocyclic ring silylene further combines with formaldehyde to form an intermediate. Because the Si： atom in intermediate shows sp3 hybridization after transition state, the intermediate isomerizes to a spiro-Si-heterocyclic ring compound involving Ge via a transition state. Simultaneously, the ring strain of the four-membered Ge-heterocyclic ring silylene makes it isomerize to a twisted four-membered ring product. The research result indicates the laws of cycloaddition reaction between X2Ge=Si： （X = H, Me, F, C1, Br, Ph, Ar...） and the asymmetric g-bonded compounds, which are significant for the synthesis of small-ring and spiro-Si-heterocyclic ring compound involving Ge The study extends the research area and enriches the research content of silvlene chemistrv.展开更多
X2Si=Ge： （X = H, Me, F, CI, Br, Ph, Ar...） is a new species. Its cycloaddition reaction is a new area for the study of germylene chemistry. The mechanism of cycloaddition reaction between singlet state Me2Si=Ge： a...X2Si=Ge： （X = H, Me, F, CI, Br, Ph, Ar...） is a new species. Its cycloaddition reaction is a new area for the study of germylene chemistry. The mechanism of cycloaddition reaction between singlet state Me2Si=Ge： and formaldehyde has been investigated with the CCSD（T）//MP2/cc-pvtz method. From the potential energy profile, it could be predicted that the reaction has one dominant reaction pathway. The reaction rule presented is that the two reactants first form a four-membered Si-heterocyclic ring germylene through the [2＋2] cycloaddition reaction. Because of the 4p unoccupied orbital of Ge： atom in the four-membered Si-heterocyclic ring germylene and the π orbital of formaldehyde form a π→p donor-acceptor bond, the four-membered Si-heterocyclic ring germylene further combines with formaldehyde to form an intermediate. Because the Ge atom in the intermediate undergoes sp^3 hybridization after transition state, then the intermediate isomerizes to a spiro-Ge-heterocyclic ring compound involving Si via a transition state. The research result indicates the laws of cycloaddition reaction between HzSi=Ge： and formaldehyde. It has important reference value for the cycloaddition reaction between X2Si=Ge： （X = H, Me, F, CI, Br, Ph, Ar…） and asymmetric to-bonded compounds, which is significant for the synthesis of small-ring and spiro-Ge-heterocyclic compounds involving Si. The study extends research area and enriches the research content of germylene chemistry.展开更多
X2Si=Sn:(X = H, Me, F, Cl, Br, Ph, Ar…) are new species of chemistry. The cycloaddition reaction of X2Si=Sn: is a new study field of stannylene chemistry. To explore the rules of cycloaddition reaction between X2Si=S...X2Si=Sn:(X = H, Me, F, Cl, Br, Ph, Ar…) are new species of chemistry. The cycloaddition reaction of X2Si=Sn: is a new study field of stannylene chemistry. To explore the rules of cycloaddition reaction between X2Si=Sn: and the symmetric p-bonded compounds, the cycloaddition reactions of Cl2Si=Sn: and ethylene were selected as model reactions in this paper.The mechanism of cycloaddition reaction between singlet Cl2Si=Sn: and ethylene has been first investigated with the MP2/GENECP(C, H, Cl, Si in 6-311++G**;Sn in LanL2dz) method in this paper. From the potential energy profile, it could be predicted that the reaction has one dominant reaction channel. The reaction rule presented is that the 5p unoccupied orbital of Sn in Cl2Si=Sn: and the π orbital of ethylene forming a p→p donor-acceptor bond, resulting in the formation of an intermediate. Instability of the intermediate makes it isomerize to a four-membered Si-heterocyclic ring stannylene. Because the 5p unoccupied orbital of Sn atom in the four-membered Si-heterocyclic ring stannylene and the π orbital of ethylene form a p→p donor-acceptor bond, the four-membered Si-heterocyclic ring stannylene further combines with ethene to form another intermediate. Because the Sn atom in the intermediate shows sp3 hybridization after transition state, the intermediate isomerizes to a Si-heterocyclic spiro-Sn-heterocyclic ring compound. The research result indicates the laws of cycloaddition reaction between X2Si=Sn: and the symmetric π-bonded compounds. The study opens up a new research field for stannylene chemistry.展开更多
Divergent synthesis of medium-sized rings with controllable ring sizes represents a longstanding challenge in organic synthesis.Herein,we developed a transition-metal-catalyzed switchable divergent cycloaddition of pa...Divergent synthesis of medium-sized rings with controllable ring sizes represents a longstanding challenge in organic synthesis.Herein,we developed a transition-metal-catalyzed switchable divergent cycloaddition of para-quinone methides and vinylethylene carbonates by controlling the steric hindrance of substituent.Different from reported alkoxide-triggered annulations,this process undergoes a regiodivergent allylation of para-quinone methides followed by 1,6-addition reaction,providing a new route to selectively synthesize seven-to ten-membered nitrogen-containing heterocycles in high yields with excellent regioselectivities.This protocol features a broad substrate scope,wide functional group tolerance as well as operational simplicity.The reaction mechanism was investigated by conducting a series of control experiments as well as DFT calculations and the origins of the regioselectivities of the cycloaddition process were rationalized.展开更多
<strong>Objective:</strong><span style="font-family:""><span style="font-family:Verdana;"> Breast cancer is a public health challenge on a global scale that is caused b...<strong>Objective:</strong><span style="font-family:""><span style="font-family:Verdana;"> Breast cancer is a public health challenge on a global scale that is caused by environmental or genetic factors. Breast cancer is affecting both males and females, but there is still a lack of effective drugs with improved potency and admissibility against breast cancer as many of the breast cancer drugs have severe side effects. </span><b><span style="font-family:Verdana;">Methods:</span></b><span style="font-family:Verdana;"> The docking approach has been used </span><span><span style="font-family:Verdana;">to find a new compound for breast cancer with more efficacy and tolerance and with lesser side effects. A ligand-based pharmacophore approach has been generated for 39 anticancer compounds with significance for the development of new drugs. </span><b><span style="font-family:Verdana;">Result:</span></b><span style="font-family:Verdana;"> Through docking, the approach found new lead compoun</span></span><span style="font-family:Verdana;">ds for breast cancer. The proposed pharmacophore model in this study contains two HBAs and one HYD</span></span><span style="font-family:Verdana;">,</span><span style="font-family:""><span style="font-family:Verdana;"> one hydrophobic domain </span><span style="font-family:Verdana;">and</span><span style="font-family:Verdana;"> two Aromatic rings</span></span><span style="font-family:""><span style="font-family:Verdana;"> and the estimated distance range is minimum to maxi</span><span style="font-family:Verdana;">mum of derived pharmacophore features.</span></span><span style="font-family:""> <b><span style="font-family:Verdana;">Conclusion:</span></b><span style="font-family:Verdana;"> Based on this research, it is proposed that these two lead compounds may be able to be used against EGFR in breast cancer. New compounds can be identified based on common features in the Pharmacophore model. 3D pharmacophore triangle could be used for further studies because this pharmacophore has better merging and in the future for more studies can suggest the same distance range of pha</span></span><span style="font-family:Verdana;">rmacophore features as this pharmacophore.</span>展开更多
Bearing ring is the crucial component of bearing. With regard to such problems as material waste, low efficiency and high energy consumption in current process of producing large bearing ring, a new process named ＂ca...Bearing ring is the crucial component of bearing. With regard to such problems as material waste, low efficiency and high energy consumption in current process of producing large bearing ring, a new process named ＂casting-rolling compound forming technology＂ is researched by taking the typical 42CrMo slew bearing as object. Through theoretical analysis, the design criteria of the main casting-rolling forming parameters are put forward at first. Then the constitutive relationship model of as-cast 42CrMo steel and its mathematical model of dynamic recrystallization are obtained according to the results of the hot compression experiment. By a coupled thermal-mechanical finite element model for radial-axial rolling of bearing ring, the fraction of dynamic recrystallization is calculated and recrystallized grains size are predicated. Meanwhile, the effects of the initial rolling temperature and feed rate of idle roll on material microstructure evolution are analyzed. Finally, the industrial rolling experiment is designed and performed, based on the simulation results. In addition, mechanical and metallographic tests are conducted on rolled bearing ring to get the mechanical parameters and metallographic structure. The experimental data and results show that the mechanical properties of bearing ring produced by casting-rolling compound forming technology are up to industrial standard, and a qualified bearing ring can be successfully formed by employing this new technology. Through the study, a process of forming large bearing ring directly by using casting ring blank is obtained, which could provide an effective theoretical guidance for manufacturing large ring parts. It also has an edge in saving material, lowering energy and improving efficiency.展开更多
A plate submerged at a certain depth underneath the sea surface has been proposed as a structure type for different purposes, including motion response reduction, wave control, and wave energy harvesting. In the prese...A plate submerged at a certain depth underneath the sea surface has been proposed as a structure type for different purposes, including motion response reduction, wave control, and wave energy harvesting. In the present study, the three-dimensional wave radiation problem is investigated in the context of the linear potential theory for a submerged ring plate in isolation or attached to a floating column as an appendage. In the latter case, the ring plate is attached at a certain distance above the column bottom. The structure is assumed to undergo a heave motion. An analytical model is developed to solve the wave radiation problem via the eigenfunction expansion method in association with the region-matching technique. With the velocity potential being available, the hydrodynamic coefficients, such as added mass and radiation damping, are obtained through the direct pressure integration. An alternative solution of radiation damping has also been developed in this study, in which the radiation damping is related to the Kochin function in the wave radiation problem. After validating the present model, numerical analysis is performed in detail to assess the influence of various plate parameters, such as the plate size and submergence depth. It is noted that the additional added mass due to the attached ring plate is larger than that when the plate is in isolation. Meanwhile, the radiation damping of the column for the heave motion can vanish at a specific wave frequency by attaching a ring plate, corresponding to a condition that there exist no progressive waves in the exterior region.展开更多
Reaction products of 2,4,6-tris(4-phenyl-phenoxy)-1,3,5-triazine derived from 4-phenylphenol cyanate ester and phenyl glycidyl ether were analyzed. In addition to an isocyanurate compound and an oxazolidone compound w...Reaction products of 2,4,6-tris(4-phenyl-phenoxy)-1,3,5-triazine derived from 4-phenylphenol cyanate ester and phenyl glycidyl ether were analyzed. In addition to an isocyanurate compound and an oxazolidone compound which were well known as reaction products of cyanate esters and epoxy resins, compounds with hybrid ring structure of cyanurate/isocyanurate were determined. Gibbs free energies of the compound having hybrid ring structure of cyanurate/isocyanurate with two isocyanurate moiety were found to be lower than that of the compound with cyanurate ring structure through calculations. Calculation data supported the existence of hybrid ring structure of cy-anurate/isocyanurate. It was revealed that isomerization from cyanurate to isocyanurate occurs via hybrid ring structure of cyanurate/isocyanurate in the reaction of aryl cyanurate and epoxy.展开更多
基金supported by the Deanship of Scientific Research,King Saud University(No.M/202) and SABIC Company
文摘Three Keggin-type heteropolyanions, namely H3PMo12O40-13H2O, （NH4）3PMo12O40·4H2O and H3PW12O40·13H2O were prepared and tested in the ring-opening polymerization reaction of tetrahydrofuran. The effects of the counter-cation （H＋, NH4＋） and the peripheral atoms （Mo, W） on the polymerization were investigated. It has been found that when the protons of H3PMo12O40·13H2O were replaced by the ammonium cations the polymerization rate decreased dramatically. Whereas, when the peripheral atoms （Mo） were replaced by their homologous （W）, the polymerization rate increased twofold. As for the viscosity average molecular weight （My） of polymer products, it was found that the high molecular weight （7930） was obtained by using H3PW12O40·13H2O. The molecular weight （My） obtained by H3PMo12O40·13H2O and （NH4）H3PMo12O40·13H2O was 6470 and 6810, respectively.
基金Supported by the National Natural Science Foundation of China
文摘Two photochromic compounds with the pyrazolonering as the photochromic functional structure, 2(1phenyl3methyl4benzoformylpyrazolone5)thiosemicarbazone(PMBPTSC) and 2(1phenyl3methyl4benzoformylpyrazolone5)smethylthiosemicarbazone(PMBPMTSC), were synthesized and characterized by elemental analysis, MS, IR spectra, NMR spectra. The crystal structure of the photocolored product of PMBPTSC was determined by single crystal XRD analysis. The results show that the photochromic phenomenon is due to the photoisomerization from enol form to keto form. Their photochromic properties were studied by powderUV reflectance spectra under the irradiation of 200—380 nm light. The firstorder rate constants of the photocoloring reaction were found to be 780×10 -3 s -1 for compound 1A and 103×10 -3 s -1 for compound 2A.
文摘The reaction of cis- 2- chloro- 4- phenyl- 5, 5- dimethyl- 1, 3. 2-dioxaghosghor inan-2- thione (Ⅰ) with methoxide or phenoxide at room temperatute takes place with retent ion of configuration. while refluxing cis- (1) and methoxide in methanol, gartial isomerization of cis-thioghosphate (2) to its trans isomer occursand an acyclic intermediate (3) is found to be involved in this grocess
基金the National Natural Science Foundation of China (20073048),NSF of Fujian province (2002F015) and the Chinese Academy of Sciences
文摘Sodium molybdate was reduced to produce ring-like compounds in the presence of carboxylic acids. Compound 1: Na8(H2O)28(H3O)+{Na(DMSO)2[MoVI10MoV8O52(OH)4(CH3C- OO)2]}11H2O (C8H103O102Na9S2Mo18, Mr = 3829.85), where the {Mo18} ring is built up by two acetic acids connecting two {Mo9} building blocks and the 1-D chain of 1 is formed through the coordinated sodium cations. Crystal data: triclinic, space group P, a = 11.3228(2), b = 15.4170(2), c = 16.7209(3) ? a = 113.006(1), b = 108.455(1), g = 92.430(1), V = 2501.98(7) 3, Z = 1, Dc = 2.542 g/cm3, F(000) = 1854, (MoKa) = 2.381 mm-1, T = 293(2) K, final R = 0.0532 and wR = 0.1203 for 7291 observed reflections with I > 2(I) from 8775 independent reflections. Compound 2: Na8(H2O)22(H3O)+{Na(DMSO)2[MoVI10MoV8O52(OH)4(C2H5COO)2]}10H2O (C10H93O94Na9- S2Mo18, Mr = 3715.79). Crystal data: monoclinic, space group C2/m, a = 18.044(1), b = 25.944(2), c = 10.4087(6) ? b = 106.613(2), V = 4669.3(5) 3, Z = 2, Dc = 2.643 g/cm3, F(000) = 3584, (MoKa) = 2.542 mm-1, T = 293(2) K, final R = 0.0536 and wR = 0.1621 for 4617 observed reflections with I > 2(I) from 5398 independent reflections. Similar to 1, the {Mo18} ring is built up by two {Mo9} building blocks that are connected up by two propanoic acids and these {Mo18} rings are further linked into a two-dimensional layer through the coordinated sodium cations.
文摘The H2Ge=Ge：, as well as and its derivatives （X2Ge=Ge：, X=H, Me, F, C1, Br, Ph, At, ...） is a kind of new species. Its cycloaddition reactions is a new area for the study of germylene chemistry. The mechanism of the cycloaddition reaction between singlet Me2Ge=Ge： and acetaldehyde was investigated with the B3LYP/6-31G＊ method in this work. From the potential energy profile, it could be predicted that the reaction has one dominant reaction pathway. The reaction rule is that the two reactants firstly form a four-membered Ge-heterocyclic ring germylene through the [2＋2] cycloaddition reaction. Because of the 4p unoccupied orbital of Ge： atom in the four-membered Ge-heterocyclic ring germylene and the ~ orbital of acetaldehyde forming a r^--~p donor-acceptor bond, the four-membered Ge-heterocyclic ring germylene further combines with acetaldehyde to form an intermedi- ate. Because the Ge atom in intermediate happens sp3 hybridization after transition state, then, intermediate isomerizes to a spiro-Ge-heterocyclic ring compound via a transition state. The research result indicates the laws of cycloaddition reaction between Me2Ge=Ge： and ac- etaldehyde, and lays the theory foundation of the cycloaddition reaction between H2Ge=Ge： and its derivatives （X2Ge=Ge：, X=H, Me, F, C1, Br, Ph, At, ...） and asymmetric ^-bonded compounds, which are significant for the synthesis of small-ring and spiro-Ge-heterocyclic ring compounds.
文摘H2Ge=Si： and its derivatives （X2Ge=Si：, X=H, Me, F, C1, Br, Ph, Ar, ...） are new species. Its cycloaddition reactions are new area for the study of silylene chemistry. The cycloaddition reaction mechanism of singlet H2Ge=Si： and formaldehyde has been investigated with the MP2/aug-cc-pVDZ method. From the potential energy profile, it could be predicted that the reaction has one dominant reaction pathway. The reaction rule is that two reactants firstly form a four-membered Ge-heterocyclic ring silylene through the [2＋2] cycloaddition reaction. Because of the 3p unoccupied orbital of Si： atom in the four-membered Ge-heterocyclic ring silylene and the π orbital of formaldehyde forming a π--p donor-acceptor bond, the four-membered Ge-heterocyclic ring silylene further combines with formaldehyde to form an intermediate. Because the Si： atom in the intermediate undergoes sp3 hybridization after transition state, then the intermediate isomerizes to a spiro-Si-heterocyclic ring compound involving Ge via a transition state. The result indicates the laws of cycloaddition reaction between H2Ge=Si： or its derivatives （X2Ge=Si：, X=H, Me, F, Cl, Br, Ph, Ar, ...） and asymmetric π-bonded compounds are significant for the synthesis of small-ring involving Si and Ge and spiro-Si-heterocyclic ring compounds involving Ge.
基金supported by the National Natural Science Foundation of China (Nos.41675127, 41475116)。
文摘Characteristics of atmospheric VOCs(volatile organic compounds) have been extensively studied in megacities in China, however, they are scarcely investigated in medium/smallsized cities in North China Plain(NCP).A comprehensive research on possible sources of VOCs was conducted in a medium-sized city of NCP, from May to September 2019.A total of 143 canister samples of 8 sites in Xuchang city were collected, and 57 VOC species were detected.The average VOC concentrations were 42.6 ± 31.6 μg/m3, with 53.7 ± 31.0 μg/m3 and 32.1 ± 27.8 μg/m^(3), in the morning and afternoon, respectively.Alkenes and aromatics contributed 80% of the total ozone formation potential(OFP).Aromatics accounted for more than 95% of secondary organic aerosol potential(SOAP).VOCs were dominated by the local emission with significant transport from the southeast direction.PMF analysis extracted 6 sources, which were combustion(33.1%), LPG usage(19.3%), vehicular exhaust & fuel evaporation(15.8%), solvent usage(15.2%), industrial(9.11%) and biogenic(7.51%), respectively and they contributed 33.4%, 17.6%, 12.9%, 18.6%, 9.28% and 8.22% to the OFP, respectively.Combustion and LPG usage were the dominant VOC sources;and combustion, solvent usage and LPG usage were the main sources of OFP in Xuchang city, which were different to megacities in China with a high contribution from vehicular exhaust, solvent usage and industry,suggesting specific control strategies on VOCs need to be implemented in medium-sized city such as Xuchang city.
基金supported by the National Natural Science Foundation of China(No.51102114)
文摘The X2Ge=Si： （X = H, Me, F, reaction is a new area for the study of silylene between singlet CI2Ge=Si： and formaldehyde CI, Br, Ph, At...） is a new species. Its cycloaddition chemistry. The mechanism of cycloaddition reaction has been investigated with CCSD（T）//MP2/6-31G＊ method. From the potential energy profile, it can be predicted that the reaction has two competitive dominant reaction pathways. The reaction rule presented is that the two reactants firstly form a four-membered Ge-heterocyclic ring silylene through the [2＋2] cycloaddition reaction. Owing to the 3p unoccupied orbital of Si： atom in the four-membered Ge-heterocyclic ring silylene and the π orbital of formaldehyde forming a π-p donor-acceptor bond, the four-membered Ge-heterocyclic ring silylene further combines with formaldehyde to form an intermediate. Because the Si： atom in intermediate shows sp3 hybridization after transition state, the intermediate isomerizes to a spiro-Si-heterocyclic ring compound involving Ge via a transition state. Simultaneously, the ring strain of the four-membered Ge-heterocyclic ring silylene makes it isomerize to a twisted four-membered ring product. The research result indicates the laws of cycloaddition reaction between X2Ge=Si： （X = H, Me, F, C1, Br, Ph, Ar...） and the asymmetric g-bonded compounds, which are significant for the synthesis of small-ring and spiro-Si-heterocyclic ring compound involving Ge The study extends the research area and enriches the research content of silvlene chemistrv.
基金supported by the National Natural Science Foundation of China(No.51102114)
文摘X2Si=Ge： （X = H, Me, F, CI, Br, Ph, Ar...） is a new species. Its cycloaddition reaction is a new area for the study of germylene chemistry. The mechanism of cycloaddition reaction between singlet state Me2Si=Ge： and formaldehyde has been investigated with the CCSD（T）//MP2/cc-pvtz method. From the potential energy profile, it could be predicted that the reaction has one dominant reaction pathway. The reaction rule presented is that the two reactants first form a four-membered Si-heterocyclic ring germylene through the [2＋2] cycloaddition reaction. Because of the 4p unoccupied orbital of Ge： atom in the four-membered Si-heterocyclic ring germylene and the π orbital of formaldehyde form a π→p donor-acceptor bond, the four-membered Si-heterocyclic ring germylene further combines with formaldehyde to form an intermediate. Because the Ge atom in the intermediate undergoes sp^3 hybridization after transition state, then the intermediate isomerizes to a spiro-Ge-heterocyclic ring compound involving Si via a transition state. The research result indicates the laws of cycloaddition reaction between HzSi=Ge： and formaldehyde. It has important reference value for the cycloaddition reaction between X2Si=Ge： （X = H, Me, F, CI, Br, Ph, Ar…） and asymmetric to-bonded compounds, which is significant for the synthesis of small-ring and spiro-Ge-heterocyclic compounds involving Si. The study extends research area and enriches the research content of germylene chemistry.
基金supported by the National Natural Science Foundation of China(No.51102114)
文摘X2Si=Sn:(X = H, Me, F, Cl, Br, Ph, Ar…) are new species of chemistry. The cycloaddition reaction of X2Si=Sn: is a new study field of stannylene chemistry. To explore the rules of cycloaddition reaction between X2Si=Sn: and the symmetric p-bonded compounds, the cycloaddition reactions of Cl2Si=Sn: and ethylene were selected as model reactions in this paper.The mechanism of cycloaddition reaction between singlet Cl2Si=Sn: and ethylene has been first investigated with the MP2/GENECP(C, H, Cl, Si in 6-311++G**;Sn in LanL2dz) method in this paper. From the potential energy profile, it could be predicted that the reaction has one dominant reaction channel. The reaction rule presented is that the 5p unoccupied orbital of Sn in Cl2Si=Sn: and the π orbital of ethylene forming a p→p donor-acceptor bond, resulting in the formation of an intermediate. Instability of the intermediate makes it isomerize to a four-membered Si-heterocyclic ring stannylene. Because the 5p unoccupied orbital of Sn atom in the four-membered Si-heterocyclic ring stannylene and the π orbital of ethylene form a p→p donor-acceptor bond, the four-membered Si-heterocyclic ring stannylene further combines with ethene to form another intermediate. Because the Sn atom in the intermediate shows sp3 hybridization after transition state, the intermediate isomerizes to a Si-heterocyclic spiro-Sn-heterocyclic ring compound. The research result indicates the laws of cycloaddition reaction between X2Si=Sn: and the symmetric π-bonded compounds. The study opens up a new research field for stannylene chemistry.
基金supportedbythe National Natural Science Foundation of China(Nos.82173664,81803342)“Shuang Chuang”Research Team of jiangsu Province(No.20182036).
文摘Divergent synthesis of medium-sized rings with controllable ring sizes represents a longstanding challenge in organic synthesis.Herein,we developed a transition-metal-catalyzed switchable divergent cycloaddition of para-quinone methides and vinylethylene carbonates by controlling the steric hindrance of substituent.Different from reported alkoxide-triggered annulations,this process undergoes a regiodivergent allylation of para-quinone methides followed by 1,6-addition reaction,providing a new route to selectively synthesize seven-to ten-membered nitrogen-containing heterocycles in high yields with excellent regioselectivities.This protocol features a broad substrate scope,wide functional group tolerance as well as operational simplicity.The reaction mechanism was investigated by conducting a series of control experiments as well as DFT calculations and the origins of the regioselectivities of the cycloaddition process were rationalized.
文摘<strong>Objective:</strong><span style="font-family:""><span style="font-family:Verdana;"> Breast cancer is a public health challenge on a global scale that is caused by environmental or genetic factors. Breast cancer is affecting both males and females, but there is still a lack of effective drugs with improved potency and admissibility against breast cancer as many of the breast cancer drugs have severe side effects. </span><b><span style="font-family:Verdana;">Methods:</span></b><span style="font-family:Verdana;"> The docking approach has been used </span><span><span style="font-family:Verdana;">to find a new compound for breast cancer with more efficacy and tolerance and with lesser side effects. A ligand-based pharmacophore approach has been generated for 39 anticancer compounds with significance for the development of new drugs. </span><b><span style="font-family:Verdana;">Result:</span></b><span style="font-family:Verdana;"> Through docking, the approach found new lead compoun</span></span><span style="font-family:Verdana;">ds for breast cancer. The proposed pharmacophore model in this study contains two HBAs and one HYD</span></span><span style="font-family:Verdana;">,</span><span style="font-family:""><span style="font-family:Verdana;"> one hydrophobic domain </span><span style="font-family:Verdana;">and</span><span style="font-family:Verdana;"> two Aromatic rings</span></span><span style="font-family:""><span style="font-family:Verdana;"> and the estimated distance range is minimum to maxi</span><span style="font-family:Verdana;">mum of derived pharmacophore features.</span></span><span style="font-family:""> <b><span style="font-family:Verdana;">Conclusion:</span></b><span style="font-family:Verdana;"> Based on this research, it is proposed that these two lead compounds may be able to be used against EGFR in breast cancer. New compounds can be identified based on common features in the Pharmacophore model. 3D pharmacophore triangle could be used for further studies because this pharmacophore has better merging and in the future for more studies can suggest the same distance range of pha</span></span><span style="font-family:Verdana;">rmacophore features as this pharmacophore.</span>
基金supported by Key Program of National Natural Science Foundation of China(Grant No.51135007)National Natural Science Foundation of China(Grant No.51075290)
文摘Bearing ring is the crucial component of bearing. With regard to such problems as material waste, low efficiency and high energy consumption in current process of producing large bearing ring, a new process named ＂casting-rolling compound forming technology＂ is researched by taking the typical 42CrMo slew bearing as object. Through theoretical analysis, the design criteria of the main casting-rolling forming parameters are put forward at first. Then the constitutive relationship model of as-cast 42CrMo steel and its mathematical model of dynamic recrystallization are obtained according to the results of the hot compression experiment. By a coupled thermal-mechanical finite element model for radial-axial rolling of bearing ring, the fraction of dynamic recrystallization is calculated and recrystallized grains size are predicated. Meanwhile, the effects of the initial rolling temperature and feed rate of idle roll on material microstructure evolution are analyzed. Finally, the industrial rolling experiment is designed and performed, based on the simulation results. In addition, mechanical and metallographic tests are conducted on rolled bearing ring to get the mechanical parameters and metallographic structure. The experimental data and results show that the mechanical properties of bearing ring produced by casting-rolling compound forming technology are up to industrial standard, and a qualified bearing ring can be successfully formed by employing this new technology. Through the study, a process of forming large bearing ring directly by using casting ring blank is obtained, which could provide an effective theoretical guidance for manufacturing large ring parts. It also has an edge in saving material, lowering energy and improving efficiency.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.51809037,51879039 and51490672)the Fundamental Research Funds for the Central Universities(Grant No.DUT16RC(4)048)
文摘A plate submerged at a certain depth underneath the sea surface has been proposed as a structure type for different purposes, including motion response reduction, wave control, and wave energy harvesting. In the present study, the three-dimensional wave radiation problem is investigated in the context of the linear potential theory for a submerged ring plate in isolation or attached to a floating column as an appendage. In the latter case, the ring plate is attached at a certain distance above the column bottom. The structure is assumed to undergo a heave motion. An analytical model is developed to solve the wave radiation problem via the eigenfunction expansion method in association with the region-matching technique. With the velocity potential being available, the hydrodynamic coefficients, such as added mass and radiation damping, are obtained through the direct pressure integration. An alternative solution of radiation damping has also been developed in this study, in which the radiation damping is related to the Kochin function in the wave radiation problem. After validating the present model, numerical analysis is performed in detail to assess the influence of various plate parameters, such as the plate size and submergence depth. It is noted that the additional added mass due to the attached ring plate is larger than that when the plate is in isolation. Meanwhile, the radiation damping of the column for the heave motion can vanish at a specific wave frequency by attaching a ring plate, corresponding to a condition that there exist no progressive waves in the exterior region.
文摘Reaction products of 2,4,6-tris(4-phenyl-phenoxy)-1,3,5-triazine derived from 4-phenylphenol cyanate ester and phenyl glycidyl ether were analyzed. In addition to an isocyanurate compound and an oxazolidone compound which were well known as reaction products of cyanate esters and epoxy resins, compounds with hybrid ring structure of cyanurate/isocyanurate were determined. Gibbs free energies of the compound having hybrid ring structure of cyanurate/isocyanurate with two isocyanurate moiety were found to be lower than that of the compound with cyanurate ring structure through calculations. Calculation data supported the existence of hybrid ring structure of cy-anurate/isocyanurate. It was revealed that isomerization from cyanurate to isocyanurate occurs via hybrid ring structure of cyanurate/isocyanurate in the reaction of aryl cyanurate and epoxy.
