The electrochemical water splitting to produce hydrogen converts electric energy into clean hydrogen energy,which is a groundbreaking concept of energy optimization.To achieve high efficiency,numerous strategies have ...The electrochemical water splitting to produce hydrogen converts electric energy into clean hydrogen energy,which is a groundbreaking concept of energy optimization.To achieve high efficiency,numerous strategies have been developed to enhance the performance of electrocatalysts.Among these,interface engineering with molecules/ions/groups,serves as a versatile approach for optimizing the performance of electrocatalysts in water splitting.On the basis of numerous achievements in high-performance electrocatalysts engineered through molecules/ions/groups at interface,a comprehensive understanding of these advancements is crucial for guiding future progress.Herein,after providing a concise overview of the background,the interface engineering via molecules/ions/groups for electrocatalytic water splitting is demonstrated from three perspectives.Firstly,the engineering of electronic state of electrocatalysts by molecules/ions/groups at interface to reduce the Gibbs free energy of the corresponding reactions.Secondly,the modification of local microenvironment surrounding electrocatalysts via molecules/ions/groups at interface to enhance the transfer of reactants and products.Thirdly,the protection of electrocatalysts with molecule/ion/group fences improves their durability,including protecting active sites from leaching and defending them against harmful species.The fundamental principles of these three aspects are outlined for each,along with pertinent comments.Finally,several research directions and challenges are proposed.展开更多
Acceptor-donor-acceptor(A-D-A)type molecules,of which the novel non-fused azacyclic end-group pyrazoli-nones were modified with chlorine substitution on the phenyl ring,were synthesized.The non-fused azacyclic end-gro...Acceptor-donor-acceptor(A-D-A)type molecules,of which the novel non-fused azacyclic end-group pyrazoli-nones were modified with chlorine substitution on the phenyl ring,were synthesized.The non-fused azacyclic end-group py-razolinones have the advantages of simple synthesis steps,low cost and environmental friendliness,compared to the classical end-group dicyanomethyleneindianone.The properties of the synthesized A-D-A type molecules with non-fused azacyclic end groups were characterized by theoretical calculation,UV-vis absorption,cyclic voltammetry,X-ray diffraction and space charge limited current.It is shown that the strong UV-vis absorptions of the synthesized A-D-A type molecules are located in the wavelength range of 500~700 nm,with a moderate band gap of nearly 1.7 eV.At the same time,the influence of end-group chlorination on the properties of A-D-A type molecules was compared and explored.It is proven that this kind of A-D-A type molecule with non-fused azacyclic end groups has the potential to be applied as interfacial modified layer of the active layer in perovskite solar cell devices.展开更多
Metal-organic frameworks(MOFs)attract broad interests in mercury(Hg)ion adsorption field,while unreasonable distribution of active groups commonly restricts their utilization efficiency.In this work,we constructed a n...Metal-organic frameworks(MOFs)attract broad interests in mercury(Hg)ion adsorption field,while unreasonable distribution of active groups commonly restricts their utilization efficiency.In this work,we constructed a new MOF(TYUST-6)with dense thiol-rich traps in the 1D pore wall.This accessible channel and rational distribution of thiols allow the smooth diffusion of Hg ions and thereby result in a high Langmuir adsorption capacity of 1347.6 mg/g,almost reaching the theoretical maximum(1444.3 mg/g).Adsorption equilibrium needs 10 and 30 min at the initial concentrations of 10 and 100 mg/L,respectively.Common co-existing ions and solution pH show almost negligible interferences on the adsorption,and adsorbent regeneration can be well achieved.Combining experimental characterizations and theoretical calculations,the thiol groups in the pore wall are proved to be the dominant interaction sites.Thus,this work reports a novel high-capacity adsorbent for Hg^(2+),and proposes a feasible guideline for designing effective adsorbents.展开更多
The ring has been a romantic fascination throughout the ages,embodying not only beauty and order but also harboring numerous undisclosed properties awaiting discovery.In the realm of supramolecular chemistry,macrocycl...The ring has been a romantic fascination throughout the ages,embodying not only beauty and order but also harboring numerous undisclosed properties awaiting discovery.In the realm of supramolecular chemistry,macrocycles,with a cyclic structure and a central cavity like a doughnut,captivate the attention of scientists[1].In 1967,Pedersen's groundbreaking revelation that alkali metal ions could"fall into"the cavities of a cyclic ether named crown ether,even in organic solvents,unveiled a novel universe of macrocycle chemistry.Since then,numerous macrocyclic structures in nature have been discovered,isolated,and scrutinized.Drawing inspiration from nature,chemists endeavor to explore the vast potential of macrocyclic compounds by designing and synthesizing artificial macrocycles with diverse structural features and recognition properties.展开更多
In organic chemistry, as defined by Abegg, Kossel, Lewis and Langmuir, compounds are normally represented using structural formulas called Lewis structures. In these structures, the octet rule is used to define the nu...In organic chemistry, as defined by Abegg, Kossel, Lewis and Langmuir, compounds are normally represented using structural formulas called Lewis structures. In these structures, the octet rule is used to define the number of covalent bonds that each atom forms with its neighbors and multiple bonds are frequent. Lewis’ octet rule has unfortunately shown limitations very early when applied to non-organic compounds: most of them remain incompatible with the “rule of eight” and location of charges is uncertain. In an attempt to unify structural formulas of octet and non-octet molecules or single-charge ions, an even-odd rule was recently proposed, together with a procedure to locate charge precisely. This even-odd rule has introduced a charge-dependent effective-valence number calculated for each atom. With this number and the number of covalent bonds of each element, two even numbers are calculated. These numbers are both used to understand and draw structuralformulas of single-covalent-bonded compounds. In the present paper, a procedure is proposed to adjust structural formulas of compounds that are commonly represented with multiple bonds. In order to keep them compatible with the even-odd rule, they will be represented using only single covalent bonds. The procedure will then describe the consequences of bond simplification on charges locations. The newly obtained representations are compared to their conventional structural formulas, i.e. single-bond representation vs. multiple-bond structures. Throughout the comparison process, charges are precisely located and assigned to specific atoms. After discussion of particular cases of compounds, the paper finally concludes that a rule limiting representations of multiplecovalent bonds to single covalent bonds, seems to be suitable for numerous known compounds.展开更多
In the course of time, numerous rules were proposed to predict how atoms connect through covalent bonds. Based on the classification of elements in the periodic table, the rule of eight was first proposed to draw form...In the course of time, numerous rules were proposed to predict how atoms connect through covalent bonds. Based on the classification of elements in the periodic table, the rule of eight was first proposed to draw formulas of organic compounds. The later named octet rule exhibited shortcomings when applied to inorganic compounds. Another rule, the rule of two, using covalent bonds between atoms, was proposed as an attempt to unify description of organic and inorganic molecules. This rule unfortunately never managed to expand the field of application of the octet rule to inorganic compounds. In order to conciliate organic and inorganic compounds, the recently put forward even-odd and the isoelectronicity rules suggest the creation of one group of compounds with pairs of electrons. These rules compass the rule of two for covalent bonds as well as the octet rule for organic compounds and suggest transforming bonds of multi-bonded compounds in order to unify representations of both groups of compounds. The aim of the present paper is fourfold: to extend the rule of two to every atom shells;to replace the well-known octet rule by the even-odd rule;to apply the isoelectronicity rule to each atom and to reduce the influence range of the charge of an atom in a compound. According to both rules, the drawing of one atom with its single-covalent bonds is described with electron pairs and charge positions. To illustrate the rules, they are applied to 3D configurations of clusters.展开更多
Building on the recent success of the even-odd rule, the present paper explores its implications by studying the very specific case of OXO compounds. These compounds are usually represented with double bonds linking t...Building on the recent success of the even-odd rule, the present paper explores its implications by studying the very specific case of OXO compounds. These compounds are usually represented with double bonds linking two oxygen atoms to a central atom—as in carbon dioxyde—yet can sometimes be drawn in a triangular structure, such as in calcium dioxyde. Measurement data moreover indicate that most OXO compounds have an angle around 120° between oxygen atoms, although that seems incompatible with triangular representations. The aim here is to unify these commonly admitted representations by linking oxygen atoms through a single bond that is longer than usual covalent bonds: an “elongated bond”. This elongated bond has the interesting effect of suppressing the need for double bonds between oxygen and the central atom. The elongated bond concept is applied to about a hundred of molecules and ions and methodically compared to classical representations. It is shown that this new representation, associated to the even-odd rule, is compatible with all studied compounds and can be used in place of their classical drawings. Its usage greatly simplifies complex concepts like resonance and separated charges in gases. Elongated bonds are also shown to be practicable with the isoelectronic rule as well as isomers, and throughout chemical reactions. This study of an especially long and wide angle bond confirms the versatility of the even-odd rule: it is not limited to compounds with short covalent bonds and can include OO covalent bond lengths of more than 200 pm and with OXO angles above 90°.展开更多
The problems of traditional concrete such as brittleness,poor toughness and short service life of concrete engineering under acid rain or marine environment need to be solved urgently.Hydrated calcium silicate(C-S-H)i...The problems of traditional concrete such as brittleness,poor toughness and short service life of concrete engineering under acid rain or marine environment need to be solved urgently.Hydrated calcium silicate(C-S-H)is a key component to improve the mechanical properties and durability of concrete.However,the traditional method of concrete material design based on empirical models or comparative tests has become a bottleneck restricting the sustainable development of concrete.The synthesis method,molecular structure and properties of C-S-H were systematically described in this paper;The interface structure and interaction of graphene oxide/calcium silicate hydrate(C-S-H/GO)were discussed.On this basis,the saturated and unsaturated transport characteristics of ions and water molecules in C-S-H/GO nanochannels under the environment of ocean and acid rain were introduced.The contents of this review provide the basis for improving the multi-scale transmission theory and microstructure design of concrete.It has important guiding significance for analyzing and improving the service life of concrete in complex environment.展开更多
The complexation reaction between borate ions and phenol-formaldehyde resol resin in aqueous solution was studied by pH measurement, small model molecules and infrared spectroscopy. The results show that the complexat...The complexation reaction between borate ions and phenol-formaldehyde resol resin in aqueous solution was studied by pH measurement, small model molecules and infrared spectroscopy. The results show that the complexation can proceed completely and rapidly at room temperature. Borate ion attacks phenol hydroxyl groups and adjacent position hydroxymethyl groups on the phenol ring of the resin, and forms the coordinate bond between boron atom in borate ion and oxygen atom in the hydroxyl groups. The complexation is a quantitative reaction. The complex is a six member ring containing two oxygens and one boron. The complexation can release hydrogen ions resulting in the decreasing pH in the resin solution.展开更多
Lewis developed a 2D-representation of molecules, charged or uncharged, known as structural formula, and stated the criteria to draw it. At the time, the vast majority of known molecules followed the octet-rule, one o...Lewis developed a 2D-representation of molecules, charged or uncharged, known as structural formula, and stated the criteria to draw it. At the time, the vast majority of known molecules followed the octet-rule, one of Lewis’s criteria. The same method was however rapidly applied to represent compounds that do not follow the octet-rule, i.e. compounds for which some of the composing atoms have greater or less than eight electrons in their valence shell. In a previous paper, an even-odd rule was proposed and shown to apply to both types of uncharged molecules. In the present paper, the even-odd rule is extended with the objective to encompass all single-bonded ions in one group: Lewis’s ions, hypo- and hypervalent ions. The base of the even-odd representation is compatible with Lewis’s diagram. Additionally, each atom is subscripted with an even number calculated by adding the valence number, the number of covalent bonds of the element, and its electrical charge. This paper describes how to calculate the latter number and in doing so, how charge and electron-pairs can actually be precisely localized. Using ions known to be compatible with Lewis’s rule of eight, the even-odd rule is compared with the former. The even-odd rule is then applied to ions known as hypo- or hypervalent. An interesting side effect of the presented rule is that charge and electron-pairs are unambiguously assigned to one of the atoms composing the single-charged ion. Ions that follow the octet rule and ions that do not, are thus reconciled in one group called “electron-paired ions” due to the absence of unpaired electrons. A future paper will focus on the connection between the even-odd rule and molecules or ions having multiple bonds.展开更多
A series of new chelating resins with incorporating heterocyclic functional groups： pyridine, thiadizole, benzothizole into macroporous chloromethylated polystyrene were synthesized via hydrophilic spacer arm of poly...A series of new chelating resins with incorporating heterocyclic functional groups： pyridine, thiadizole, benzothizole into macroporous chloromethylated polystyrene were synthesized via hydrophilic spacer arm of polyethylene glycol containing sulfur. These chelating resins were found to show high adsorption capacities for Ag^＋, Hg^2＋, Au^3＋ and Pd^2＋, and the presence of spacer arm can enhance adsorption ability due to increase the hydrophilicity of the chelating resins.展开更多
A thermodynamic model for predicting the equilibrium oxygens of 304 stainless steel was developed based on the theory of slag-steel equilibrium,the law of mass conservation,and the ion and molecule coexistence theory....A thermodynamic model for predicting the equilibrium oxygens of 304 stainless steel was developed based on the theory of slag-steel equilibrium,the law of mass conservation,and the ion and molecule coexistence theory.In the developed model,the Fe-Cr-Mn-Si-Al-S-O-melts reaction system and CaO-MgO-CaF_(2)-FeO-MnO-Al_(2)O_(3)-SiO_(2)-Cr2O_(3)slags were considered.The oxygen contents calculated by the model are in good agreement with experimental results and reference data.The equilibrium oxygen contents in 304 stainless steel mainly decrease with increasing binary basicity(w(CaO)/w(SiO_(2)),where w(i)is the mass percentage of component i)and decreasing temperature.Controlling binary basicity at 2.0 while maintaining temperatures lower than 1823 K will keep the oxygen contents in the 304 stainless steel lower than 15×10^(-6).The equilibrium oxygen contents may also be decreased with increasing content of MgO in slags,which is more significant at lower binary basicity.Besides,a small amount of FeO,MnO,and Al_(2)O_(3)(about 0-2.5 wt.%)in slags has little effect on equilibrium oxygen contents.Furthermore,it is found that the[C]-[O]reaction may occur during refining process but will not significantly affect the equilibrium oxygen contents.展开更多
A new method on constructing analytical potential energy functions is presented, and then a relatively universal analytical potential energy function for precisely calculating the spectra of ＇iatomic molecules and io...A new method on constructing analytical potential energy functions is presented, and then a relatively universal analytical potential energy function for precisely calculating the spectra of ＇iatomic molecules and ions is derived. Furthermore, six kinds of common potential energy curves containing three main potential curves i,e. steady state, metastable state and repulsive state are obtained from this potential energy function. Finally, spectroscopic parameters of thirteen diatomic molecules and ions including BeD-X^2∑＋, BeT-X^2∑^＋ and Na2-X^1∑g^＋ etc are calculated by using the potential function, as a consequence, all calculation results are in good agreement with experimental data.展开更多
Several of new chelating resins containing sulfoxide and heterocyclic functional groups （3-aminopyridine and 2-mercaptobenzothiazole） based on macroporous chloromethylated polystyrene were synthesized and characteri...Several of new chelating resins containing sulfoxide and heterocyclic functional groups （3-aminopyridine and 2-mercaptobenzothiazole） based on macroporous chloromethylated polystyrene were synthesized and characterized by elemental analysis and infrared spectra. Their adsorption capacities towards Zn^2＋, Cu^2＋, Pb^2＋, Hg^2＋ and Ag^＋ at pH 3.0 and 6.0 were investigated in detail. It was found that the adsorption capacities of the resins containing bis[（3-pyridylaminoethyl）sulfoxide or （2-benzothiazolylthioethyl）sulfoxide for the above ions were higher than that on ones containing single above-mentioned groups.展开更多
Oxygen-containing functional groups were found to e ectively boost the K^(+)storage performance of carbonaceous materials,however,the mechanism behind the performance enhancement remains unclear.Herein,we report highe...Oxygen-containing functional groups were found to e ectively boost the K^(+)storage performance of carbonaceous materials,however,the mechanism behind the performance enhancement remains unclear.Herein,we report higher rate capability and better long-term cycle performance employing oxygen-doped graphite oxide(GO)as the anode material for potassium ion batteries(PIBs),compared to the raw graphite.The in situ Raman spectroscopy elucidates the adsorption-intercalation hybrid K^(+)storage mechanism,assigning the capacity enhancement to be mainly correlated with reversible K^(+)adsorption/desorption at the newly introduced oxygen sites.It is unraveled that the C=O and COOH rather than C-O-C and OH groups contribute to the capacity enhancement.Based on in situ Fourier transform infrared(FT-IR)spectra and in situ electrochemical impedance spectroscopy(EIS),it is found that the oxygen-containing functional groups regulate the components of solid electrolyte interphase(SEI),leading to the formation of highly conductive,intact and robust SEI.Through the systematic investigations,we hereby uncover the K^(+)storage mechanism of GO-based PIB,and establish a clear relationship between the types/contents of oxygen functional groups and the regulated composition of SEI.展开更多
In this paper, a new method on constructing analytical potential energy functions is pre-sented, and from this a analytical potential en-ergy function applied to both neutral diatomic molecules and charged diatomic mo...In this paper, a new method on constructing analytical potential energy functions is pre-sented, and from this a analytical potential en-ergy function applied to both neutral diatomic molecules and charged diatomic molecular ions is obtained. This potential energy function in-cludes three dimensionless undetermined pa-rameters which can be determined uniquely by solving linear equations with the experimental spectroscopic parameters of molecules. The solutions of the dimensionless undetermined parameters are real numbers rather than com-plex numbers, this ensures that the analytical potential energy function has extensive uni-versality. Finally, the potential energy function is examined with four kinds of diatomic molecules or ions—homonuclear neutral diatomic mole-cule , and , homonuclear charged diatomic molecular ion , and , heter-nuclear neutral diatomic Molecule , and , heternuclear ch- arged diatomic Molecular ion , and ,as a conseque- nce, good results are obtained.展开更多
When writing equations of chemical dissociation, students and scholars are taught two fundamental rules to balance the equation. On both sides of the equation, the types of elements and their quantity are conserved, a...When writing equations of chemical dissociation, students and scholars are taught two fundamental rules to balance the equation. On both sides of the equation, the types of elements and their quantity are conserved, as well as the global electrical charge. This paper introduces additional methods during dissociation of gaseous compounds, to precisely describe how electrical charges locally move and how bonding structures are modified. Specific rules revolving around electrons pairs displacements are developed and applied to about 150 dissociations of small gaseous molecules using atoms from the three first rows of the periodic table. Results obtained tend to demonstrate the relevance of these tools for chemists.展开更多
Background:Human natural killer(NK)cells have attracted widespread attention as a potential adoptive cell therapy(ACT).However,the therapeutic effects of NK cell infusion in patients with solid tumors are limited.Ther...Background:Human natural killer(NK)cells have attracted widespread attention as a potential adoptive cell therapy(ACT).However,the therapeutic effects of NK cell infusion in patients with solid tumors are limited.There is an urgent need to explore a suitable new treatment plan to overcome weaknesses and support the superior therapeutic activity of NK cells.Methods:In this study,the mechanisms underlying the susceptibility of gastric cancer(GC)cell lines AGS,HGC-27,and NCI-N87 to NK cell-mediated cytotoxicity were explored.Results:Lactic dehydrogenase(LDH)release assays showed that all three GC cell lines were susceptible to the umbilical cord blood NK(UCB-NK)cells,and HGC-27 cells with high CD56 expression were the most sensitive to UCB-NK,followed by NCI-N87 and AGS.When the expression of CD56 in HGC-27 cells decreased,the lytic activity of NK cells in HGC-27 cells was abating.In addition,combining oxaliplatin with NK cells produced additive anti-tumor effects in vitro,which may have resulted from oxaliplatin-induced NK group 2 member D(NKG2DL)upregulation in GC cells.These results of cytotoxicity activity showed that inhibition of CD56 expression might suppress the sensitivity of GC cells to NK cell-mediated cytotoxicity,and upregulation of the expression of NKG2DL on the surface of GC cells by oxaliplatin could enhance the killing sensitivity of NK cells.Conclusion:Collectively,our study provides a deeper theoretical foundation and a better therapeutic strategy for NK cell immunotherapy in the treatment of human GC.展开更多
A universal thermodynamic model of calculating mass action concentrations for structural units or ion couples in ternary and binary strong electrolyte aqueous solution was developed based on the ion and molecule coexi...A universal thermodynamic model of calculating mass action concentrations for structural units or ion couples in ternary and binary strong electrolyte aqueous solution was developed based on the ion and molecule coexistence theory and verified in four kinds of binary aqueous solutions and two kinds of ternary aqueous solutions. The calculated mass action concentrations of structural units or ion couples in four binary aqueous solutions and two ternary solutions at 298.15 K have good agreement with the reported activity data from literatures after shifting the standard state and concentration unit. Therefore, the calculated mass action concentrations of structural units or ion couples from the developed universal thermodynamic model for ternary and binary aqueous solutions can be applied to predict reaction ability of components in ternary and binary strong electrolyte aqueous solutions. It is also proved that the assumptions applied in the developed thermodynamic model are correct and reasonable, i.e., strong electrolyte aqueous solution is composed of cations and anions as simple ions, H2O as simple molecule and other hydrous salt compounds as complex molecules. The calculated mass action concentrations of structural units or ion couples in ternary and binary strong electrolyte aqueous solutions strictly follow the mass action law.展开更多
The rate constants of the nucleophilic reactions between amines and benzhydrylium ions were calculated using first-principles theoretical methods. Solvation models including PCM, CPCM, and COSMORS, as well as differen...The rate constants of the nucleophilic reactions between amines and benzhydrylium ions were calculated using first-principles theoretical methods. Solvation models including PCM, CPCM, and COSMORS, as well as different types of atomic radii including UA0, UAKS, UAHF, Bondi, and UFF, and several single-point energy calculation methods （B3LYP, B3P86, B3PW91, BHANDH, PBEPBE, BMK, M06, MP2, and ONIOM method） were examined. By comparing the correlation between experimental rate constants and the calculated values, the ONIOM（CCSD（T）/6-311＋＋G（2df,2p）：B3LYP/6-311＋＋G（2df,2p））//B3LYP/6- 31G（d）/PCM/UFF） method was found to perform the best. This method was then employed to calculate the rate constants of the reactions between diverse amines and diarylcarbenium ions. The calculated rate constants for 65 reactions of amines with diarylcarbenium ions are in agreement with the experimental values, indicating that it is feasible to predict the rate constant of a reaction between an amine and a diarylcarbenium ion through ab initio calculation.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22071069,22090050,22176180,21874121 and 21974128)the National Key Research and Development Program of China(Nos.2018YFE0206900 and 2021YFA1200400)+2 种基金Zhejiang Provincial Natural Science Foundation of China under Grant(Nos.LY20B050002 and LD21B050001)Hubei Provincial Natural Science Foundation of China(No.2020CFA037)the Foundation of Basic and Applied Basic Research of Guangdong Province(No.2019B1515120087).
文摘The electrochemical water splitting to produce hydrogen converts electric energy into clean hydrogen energy,which is a groundbreaking concept of energy optimization.To achieve high efficiency,numerous strategies have been developed to enhance the performance of electrocatalysts.Among these,interface engineering with molecules/ions/groups,serves as a versatile approach for optimizing the performance of electrocatalysts in water splitting.On the basis of numerous achievements in high-performance electrocatalysts engineered through molecules/ions/groups at interface,a comprehensive understanding of these advancements is crucial for guiding future progress.Herein,after providing a concise overview of the background,the interface engineering via molecules/ions/groups for electrocatalytic water splitting is demonstrated from three perspectives.Firstly,the engineering of electronic state of electrocatalysts by molecules/ions/groups at interface to reduce the Gibbs free energy of the corresponding reactions.Secondly,the modification of local microenvironment surrounding electrocatalysts via molecules/ions/groups at interface to enhance the transfer of reactants and products.Thirdly,the protection of electrocatalysts with molecule/ion/group fences improves their durability,including protecting active sites from leaching and defending them against harmful species.The fundamental principles of these three aspects are outlined for each,along with pertinent comments.Finally,several research directions and challenges are proposed.
文摘Acceptor-donor-acceptor(A-D-A)type molecules,of which the novel non-fused azacyclic end-group pyrazoli-nones were modified with chlorine substitution on the phenyl ring,were synthesized.The non-fused azacyclic end-group py-razolinones have the advantages of simple synthesis steps,low cost and environmental friendliness,compared to the classical end-group dicyanomethyleneindianone.The properties of the synthesized A-D-A type molecules with non-fused azacyclic end groups were characterized by theoretical calculation,UV-vis absorption,cyclic voltammetry,X-ray diffraction and space charge limited current.It is shown that the strong UV-vis absorptions of the synthesized A-D-A type molecules are located in the wavelength range of 500~700 nm,with a moderate band gap of nearly 1.7 eV.At the same time,the influence of end-group chlorination on the properties of A-D-A type molecules was compared and explored.It is proven that this kind of A-D-A type molecule with non-fused azacyclic end groups has the potential to be applied as interfacial modified layer of the active layer in perovskite solar cell devices.
基金supported by the National Natural Science Foundation of China(No.22208230)Fundamental Research Program of Shanxi Province(No.202103021223281)。
文摘Metal-organic frameworks(MOFs)attract broad interests in mercury(Hg)ion adsorption field,while unreasonable distribution of active groups commonly restricts their utilization efficiency.In this work,we constructed a new MOF(TYUST-6)with dense thiol-rich traps in the 1D pore wall.This accessible channel and rational distribution of thiols allow the smooth diffusion of Hg ions and thereby result in a high Langmuir adsorption capacity of 1347.6 mg/g,almost reaching the theoretical maximum(1444.3 mg/g).Adsorption equilibrium needs 10 and 30 min at the initial concentrations of 10 and 100 mg/L,respectively.Common co-existing ions and solution pH show almost negligible interferences on the adsorption,and adsorbent regeneration can be well achieved.Combining experimental characterizations and theoretical calculations,the thiol groups in the pore wall are proved to be the dominant interaction sites.Thus,this work reports a novel high-capacity adsorbent for Hg^(2+),and proposes a feasible guideline for designing effective adsorbents.
文摘The ring has been a romantic fascination throughout the ages,embodying not only beauty and order but also harboring numerous undisclosed properties awaiting discovery.In the realm of supramolecular chemistry,macrocycles,with a cyclic structure and a central cavity like a doughnut,captivate the attention of scientists[1].In 1967,Pedersen's groundbreaking revelation that alkali metal ions could"fall into"the cavities of a cyclic ether named crown ether,even in organic solvents,unveiled a novel universe of macrocycle chemistry.Since then,numerous macrocyclic structures in nature have been discovered,isolated,and scrutinized.Drawing inspiration from nature,chemists endeavor to explore the vast potential of macrocyclic compounds by designing and synthesizing artificial macrocycles with diverse structural features and recognition properties.
文摘In organic chemistry, as defined by Abegg, Kossel, Lewis and Langmuir, compounds are normally represented using structural formulas called Lewis structures. In these structures, the octet rule is used to define the number of covalent bonds that each atom forms with its neighbors and multiple bonds are frequent. Lewis’ octet rule has unfortunately shown limitations very early when applied to non-organic compounds: most of them remain incompatible with the “rule of eight” and location of charges is uncertain. In an attempt to unify structural formulas of octet and non-octet molecules or single-charge ions, an even-odd rule was recently proposed, together with a procedure to locate charge precisely. This even-odd rule has introduced a charge-dependent effective-valence number calculated for each atom. With this number and the number of covalent bonds of each element, two even numbers are calculated. These numbers are both used to understand and draw structuralformulas of single-covalent-bonded compounds. In the present paper, a procedure is proposed to adjust structural formulas of compounds that are commonly represented with multiple bonds. In order to keep them compatible with the even-odd rule, they will be represented using only single covalent bonds. The procedure will then describe the consequences of bond simplification on charges locations. The newly obtained representations are compared to their conventional structural formulas, i.e. single-bond representation vs. multiple-bond structures. Throughout the comparison process, charges are precisely located and assigned to specific atoms. After discussion of particular cases of compounds, the paper finally concludes that a rule limiting representations of multiplecovalent bonds to single covalent bonds, seems to be suitable for numerous known compounds.
文摘In the course of time, numerous rules were proposed to predict how atoms connect through covalent bonds. Based on the classification of elements in the periodic table, the rule of eight was first proposed to draw formulas of organic compounds. The later named octet rule exhibited shortcomings when applied to inorganic compounds. Another rule, the rule of two, using covalent bonds between atoms, was proposed as an attempt to unify description of organic and inorganic molecules. This rule unfortunately never managed to expand the field of application of the octet rule to inorganic compounds. In order to conciliate organic and inorganic compounds, the recently put forward even-odd and the isoelectronicity rules suggest the creation of one group of compounds with pairs of electrons. These rules compass the rule of two for covalent bonds as well as the octet rule for organic compounds and suggest transforming bonds of multi-bonded compounds in order to unify representations of both groups of compounds. The aim of the present paper is fourfold: to extend the rule of two to every atom shells;to replace the well-known octet rule by the even-odd rule;to apply the isoelectronicity rule to each atom and to reduce the influence range of the charge of an atom in a compound. According to both rules, the drawing of one atom with its single-covalent bonds is described with electron pairs and charge positions. To illustrate the rules, they are applied to 3D configurations of clusters.
文摘Building on the recent success of the even-odd rule, the present paper explores its implications by studying the very specific case of OXO compounds. These compounds are usually represented with double bonds linking two oxygen atoms to a central atom—as in carbon dioxyde—yet can sometimes be drawn in a triangular structure, such as in calcium dioxyde. Measurement data moreover indicate that most OXO compounds have an angle around 120° between oxygen atoms, although that seems incompatible with triangular representations. The aim here is to unify these commonly admitted representations by linking oxygen atoms through a single bond that is longer than usual covalent bonds: an “elongated bond”. This elongated bond has the interesting effect of suppressing the need for double bonds between oxygen and the central atom. The elongated bond concept is applied to about a hundred of molecules and ions and methodically compared to classical representations. It is shown that this new representation, associated to the even-odd rule, is compatible with all studied compounds and can be used in place of their classical drawings. Its usage greatly simplifies complex concepts like resonance and separated charges in gases. Elongated bonds are also shown to be practicable with the isoelectronic rule as well as isomers, and throughout chemical reactions. This study of an especially long and wide angle bond confirms the versatility of the even-odd rule: it is not limited to compounds with short covalent bonds and can include OO covalent bond lengths of more than 200 pm and with OXO angles above 90°.
基金This work was supported by a Doctoral program of Zhejiang University of science and technology(F701104L08)。
文摘The problems of traditional concrete such as brittleness,poor toughness and short service life of concrete engineering under acid rain or marine environment need to be solved urgently.Hydrated calcium silicate(C-S-H)is a key component to improve the mechanical properties and durability of concrete.However,the traditional method of concrete material design based on empirical models or comparative tests has become a bottleneck restricting the sustainable development of concrete.The synthesis method,molecular structure and properties of C-S-H were systematically described in this paper;The interface structure and interaction of graphene oxide/calcium silicate hydrate(C-S-H/GO)were discussed.On this basis,the saturated and unsaturated transport characteristics of ions and water molecules in C-S-H/GO nanochannels under the environment of ocean and acid rain were introduced.The contents of this review provide the basis for improving the multi-scale transmission theory and microstructure design of concrete.It has important guiding significance for analyzing and improving the service life of concrete in complex environment.
文摘The complexation reaction between borate ions and phenol-formaldehyde resol resin in aqueous solution was studied by pH measurement, small model molecules and infrared spectroscopy. The results show that the complexation can proceed completely and rapidly at room temperature. Borate ion attacks phenol hydroxyl groups and adjacent position hydroxymethyl groups on the phenol ring of the resin, and forms the coordinate bond between boron atom in borate ion and oxygen atom in the hydroxyl groups. The complexation is a quantitative reaction. The complex is a six member ring containing two oxygens and one boron. The complexation can release hydrogen ions resulting in the decreasing pH in the resin solution.
文摘Lewis developed a 2D-representation of molecules, charged or uncharged, known as structural formula, and stated the criteria to draw it. At the time, the vast majority of known molecules followed the octet-rule, one of Lewis’s criteria. The same method was however rapidly applied to represent compounds that do not follow the octet-rule, i.e. compounds for which some of the composing atoms have greater or less than eight electrons in their valence shell. In a previous paper, an even-odd rule was proposed and shown to apply to both types of uncharged molecules. In the present paper, the even-odd rule is extended with the objective to encompass all single-bonded ions in one group: Lewis’s ions, hypo- and hypervalent ions. The base of the even-odd representation is compatible with Lewis’s diagram. Additionally, each atom is subscripted with an even number calculated by adding the valence number, the number of covalent bonds of the element, and its electrical charge. This paper describes how to calculate the latter number and in doing so, how charge and electron-pairs can actually be precisely localized. Using ions known to be compatible with Lewis’s rule of eight, the even-odd rule is compared with the former. The even-odd rule is then applied to ions known as hypo- or hypervalent. An interesting side effect of the presented rule is that charge and electron-pairs are unambiguously assigned to one of the atoms composing the single-charged ion. Ions that follow the octet rule and ions that do not, are thus reconciled in one group called “electron-paired ions” due to the absence of unpaired electrons. A future paper will focus on the connection between the even-odd rule and molecules or ions having multiple bonds.
基金The authors are grateful to the financial support by the Postdoctoral Science Foundation of China(No.2003034330)the Science Foundation for mid-youth elite of Shangdong Province+1 种基金the Natural Science Foundation of Shangdong Province(No.Q99B15)the National Natural Science Foundation of China(No.2906008)
文摘A series of new chelating resins with incorporating heterocyclic functional groups： pyridine, thiadizole, benzothizole into macroporous chloromethylated polystyrene were synthesized via hydrophilic spacer arm of polyethylene glycol containing sulfur. These chelating resins were found to show high adsorption capacities for Ag^＋, Hg^2＋, Au^3＋ and Pd^2＋, and the presence of spacer arm can enhance adsorption ability due to increase the hydrophilicity of the chelating resins.
基金This work was financially supported by Key R&D Plan of Shandong Province in 2021(Grant No.2021CXGC010209).
文摘A thermodynamic model for predicting the equilibrium oxygens of 304 stainless steel was developed based on the theory of slag-steel equilibrium,the law of mass conservation,and the ion and molecule coexistence theory.In the developed model,the Fe-Cr-Mn-Si-Al-S-O-melts reaction system and CaO-MgO-CaF_(2)-FeO-MnO-Al_(2)O_(3)-SiO_(2)-Cr2O_(3)slags were considered.The oxygen contents calculated by the model are in good agreement with experimental results and reference data.The equilibrium oxygen contents in 304 stainless steel mainly decrease with increasing binary basicity(w(CaO)/w(SiO_(2)),where w(i)is the mass percentage of component i)and decreasing temperature.Controlling binary basicity at 2.0 while maintaining temperatures lower than 1823 K will keep the oxygen contents in the 304 stainless steel lower than 15×10^(-6).The equilibrium oxygen contents may also be decreased with increasing content of MgO in slags,which is more significant at lower binary basicity.Besides,a small amount of FeO,MnO,and Al_(2)O_(3)(about 0-2.5 wt.%)in slags has little effect on equilibrium oxygen contents.Furthermore,it is found that the[C]-[O]reaction may occur during refining process but will not significantly affect the equilibrium oxygen contents.
基金the National Natural Science Foundation of China (40274044)
文摘A new method on constructing analytical potential energy functions is presented, and then a relatively universal analytical potential energy function for precisely calculating the spectra of ＇iatomic molecules and ions is derived. Furthermore, six kinds of common potential energy curves containing three main potential curves i,e. steady state, metastable state and repulsive state are obtained from this potential energy function. Finally, spectroscopic parameters of thirteen diatomic molecules and ions including BeD-X^2∑＋, BeT-X^2∑^＋ and Na2-X^1∑g^＋ etc are calculated by using the potential function, as a consequence, all calculation results are in good agreement with experimental data.
基金The authors are grateful for the financial support by the Postdoctoral Science Foundation of China （No. 2003034330）the Science Foundation for mld-youth elite of Shandong Province+3 种基金the Nature Science Foundation of Shandong Province （No. Y2005F11 and No. 2005BS11010）the Nature Science Foundation of Yantai Normal University （No. 032912, 20052901, 042920） Educational Project for Postgraduate of Yantai Normal University （No. YD05001）Applied Project of Educational Bureau of Shandong Province （No. J05D03, J04B02）.
文摘Several of new chelating resins containing sulfoxide and heterocyclic functional groups （3-aminopyridine and 2-mercaptobenzothiazole） based on macroporous chloromethylated polystyrene were synthesized and characterized by elemental analysis and infrared spectra. Their adsorption capacities towards Zn^2＋, Cu^2＋, Pb^2＋, Hg^2＋ and Ag^＋ at pH 3.0 and 6.0 were investigated in detail. It was found that the adsorption capacities of the resins containing bis[（3-pyridylaminoethyl）sulfoxide or （2-benzothiazolylthioethyl）sulfoxide for the above ions were higher than that on ones containing single above-mentioned groups.
基金financially supported by the National Natural Science Foundation of China(51802091,51902102,22075074)Outstanding Young Scientists Research Funds from Hunan Province(2020JJ2004)+2 种基金Major Science and Technology Program of Hunan Province(2020WK2013)Creative Research Funds from Hunan Province(2018RS3046)Natural Science Foundation of Hunan Province(2020JJ5035)。
文摘Oxygen-containing functional groups were found to e ectively boost the K^(+)storage performance of carbonaceous materials,however,the mechanism behind the performance enhancement remains unclear.Herein,we report higher rate capability and better long-term cycle performance employing oxygen-doped graphite oxide(GO)as the anode material for potassium ion batteries(PIBs),compared to the raw graphite.The in situ Raman spectroscopy elucidates the adsorption-intercalation hybrid K^(+)storage mechanism,assigning the capacity enhancement to be mainly correlated with reversible K^(+)adsorption/desorption at the newly introduced oxygen sites.It is unraveled that the C=O and COOH rather than C-O-C and OH groups contribute to the capacity enhancement.Based on in situ Fourier transform infrared(FT-IR)spectra and in situ electrochemical impedance spectroscopy(EIS),it is found that the oxygen-containing functional groups regulate the components of solid electrolyte interphase(SEI),leading to the formation of highly conductive,intact and robust SEI.Through the systematic investigations,we hereby uncover the K^(+)storage mechanism of GO-based PIB,and establish a clear relationship between the types/contents of oxygen functional groups and the regulated composition of SEI.
文摘In this paper, a new method on constructing analytical potential energy functions is pre-sented, and from this a analytical potential en-ergy function applied to both neutral diatomic molecules and charged diatomic molecular ions is obtained. This potential energy function in-cludes three dimensionless undetermined pa-rameters which can be determined uniquely by solving linear equations with the experimental spectroscopic parameters of molecules. The solutions of the dimensionless undetermined parameters are real numbers rather than com-plex numbers, this ensures that the analytical potential energy function has extensive uni-versality. Finally, the potential energy function is examined with four kinds of diatomic molecules or ions—homonuclear neutral diatomic mole-cule , and , homonuclear charged diatomic molecular ion , and , heter-nuclear neutral diatomic Molecule , and , heternuclear ch- arged diatomic Molecular ion , and ,as a conseque- nce, good results are obtained.
文摘When writing equations of chemical dissociation, students and scholars are taught two fundamental rules to balance the equation. On both sides of the equation, the types of elements and their quantity are conserved, as well as the global electrical charge. This paper introduces additional methods during dissociation of gaseous compounds, to precisely describe how electrical charges locally move and how bonding structures are modified. Specific rules revolving around electrons pairs displacements are developed and applied to about 150 dissociations of small gaseous molecules using atoms from the three first rows of the periodic table. Results obtained tend to demonstrate the relevance of these tools for chemists.
基金supported by the CAMS Innovation Fund for Medical Sciences(Grants:2021-I2M-1-070)National Natural Science Foundation of China(Grants 82373767).
文摘Background:Human natural killer(NK)cells have attracted widespread attention as a potential adoptive cell therapy(ACT).However,the therapeutic effects of NK cell infusion in patients with solid tumors are limited.There is an urgent need to explore a suitable new treatment plan to overcome weaknesses and support the superior therapeutic activity of NK cells.Methods:In this study,the mechanisms underlying the susceptibility of gastric cancer(GC)cell lines AGS,HGC-27,and NCI-N87 to NK cell-mediated cytotoxicity were explored.Results:Lactic dehydrogenase(LDH)release assays showed that all three GC cell lines were susceptible to the umbilical cord blood NK(UCB-NK)cells,and HGC-27 cells with high CD56 expression were the most sensitive to UCB-NK,followed by NCI-N87 and AGS.When the expression of CD56 in HGC-27 cells decreased,the lytic activity of NK cells in HGC-27 cells was abating.In addition,combining oxaliplatin with NK cells produced additive anti-tumor effects in vitro,which may have resulted from oxaliplatin-induced NK group 2 member D(NKG2DL)upregulation in GC cells.These results of cytotoxicity activity showed that inhibition of CD56 expression might suppress the sensitivity of GC cells to NK cell-mediated cytotoxicity,and upregulation of the expression of NKG2DL on the surface of GC cells by oxaliplatin could enhance the killing sensitivity of NK cells.Conclusion:Collectively,our study provides a deeper theoretical foundation and a better therapeutic strategy for NK cell immunotherapy in the treatment of human GC.
基金Project supported by Publication Foundation of National Science and Technology Academic Books of China
文摘A universal thermodynamic model of calculating mass action concentrations for structural units or ion couples in ternary and binary strong electrolyte aqueous solution was developed based on the ion and molecule coexistence theory and verified in four kinds of binary aqueous solutions and two kinds of ternary aqueous solutions. The calculated mass action concentrations of structural units or ion couples in four binary aqueous solutions and two ternary solutions at 298.15 K have good agreement with the reported activity data from literatures after shifting the standard state and concentration unit. Therefore, the calculated mass action concentrations of structural units or ion couples from the developed universal thermodynamic model for ternary and binary aqueous solutions can be applied to predict reaction ability of components in ternary and binary strong electrolyte aqueous solutions. It is also proved that the assumptions applied in the developed thermodynamic model are correct and reasonable, i.e., strong electrolyte aqueous solution is composed of cations and anions as simple ions, H2O as simple molecule and other hydrous salt compounds as complex molecules. The calculated mass action concentrations of structural units or ion couples in ternary and binary strong electrolyte aqueous solutions strictly follow the mass action law.
文摘The rate constants of the nucleophilic reactions between amines and benzhydrylium ions were calculated using first-principles theoretical methods. Solvation models including PCM, CPCM, and COSMORS, as well as different types of atomic radii including UA0, UAKS, UAHF, Bondi, and UFF, and several single-point energy calculation methods （B3LYP, B3P86, B3PW91, BHANDH, PBEPBE, BMK, M06, MP2, and ONIOM method） were examined. By comparing the correlation between experimental rate constants and the calculated values, the ONIOM（CCSD（T）/6-311＋＋G（2df,2p）：B3LYP/6-311＋＋G（2df,2p））//B3LYP/6- 31G（d）/PCM/UFF） method was found to perform the best. This method was then employed to calculate the rate constants of the reactions between diverse amines and diarylcarbenium ions. The calculated rate constants for 65 reactions of amines with diarylcarbenium ions are in agreement with the experimental values, indicating that it is feasible to predict the rate constant of a reaction between an amine and a diarylcarbenium ion through ab initio calculation.
