A one-pot method for the preparation of g-C3N4/reduced graphene oxide（rGO） composite photocatalysts with controllable band structures is presented.The photocatalysts are characterized by Fouirer transform infrared s...A one-pot method for the preparation of g-C3N4/reduced graphene oxide（rGO） composite photocatalysts with controllable band structures is presented.The photocatalysts are characterized by Fouirer transform infrared spectroscopy,X-ray diffraction,scanning electron microscope,transmission electron microscope,and Mott-Schottky analysis.The valance band（VB） of g-C3N4 exhibits a noticeable positive shift upon hybridizing with rGO,and thus results in a strong photo-oxidation ability.The g-C3N4/rGO composites show a higher photodegradation activity for 2,4-dichlorophenol（2,4-DCP） and rhodamine B（RhB） under visible light irradiation（λ≥420 ran）.The g-C3N4/rGO-1sample exhibits the highest photocatalytic activity,which is 1.49 and 1.52 times higher than that of bulk g-C3N4 for 2,4-DCP and 1.52 times degradation,respectively.The enhanced photocatalytic activity for g-C3N4 originates from the improved visible light usage,enhanced electronic conductivity and photo-oxidation ability by the formed strong π-π stacking interactions with rGO.展开更多
Unconsolidated sandstone reservoirs are most susceptible to sand production that leads to a dramatic oil production decline.In this study,the poly(4-vinyl pyridine)(P_(4)VP)incorporated with self-aggregating behavior ...Unconsolidated sandstone reservoirs are most susceptible to sand production that leads to a dramatic oil production decline.In this study,the poly(4-vinyl pyridine)(P_(4)VP)incorporated with self-aggregating behavior was proposed for sand migration control.The P_(4)VP could aggregate sand grains spontaneously throughπ-πstacking interactions to withstand the drag forces sufficiently.The influential factors on the self-aggregating behavior of the P_(4)VP were evaluated by adhesion force test.The adsorption as well as desorption behavior of P_(4)VP on sand grains was characterized by scanning electron microscopy and adhesion force test at different pH conditions.The result indicated that the pH altered the forms of surface silanol groups on sand grains,which in turn affected the adsorption process of P_(4)VP.The spontaneous dimerization of P_(4)VP molecules resulting from theπ-πstacking interaction was demonstrated by reduced density gradient analysis,which contributed to the self-aggregating behavior and the thermally reversible characteristic of the P_(4)VP.Dynamic sand stabilization test revealed that the P_(4)VP showed wide pH and temperature ranges of application.The production of sands can be mitigated effectively at 20-130℃ within the pH range of 4-8.展开更多
The reaction of 6,7-dicyanodipyridoquinoxaline （DICNQ） with AgNO3 in a 1：1 molar ratio by solution method gave a new complex [Ag（DICNQ）2]NO3 1. Single-crystal X-ray diffraction analysis reveals that the complex c...The reaction of 6,7-dicyanodipyridoquinoxaline （DICNQ） with AgNO3 in a 1：1 molar ratio by solution method gave a new complex [Ag（DICNQ）2]NO3 1. Single-crystal X-ray diffraction analysis reveals that the complex crystallizes in the space group Ibca of orthorhombic system with eight formula units in a cell. Crystal data for 1： a = 15.7055（17）, b = 18.411（2）, c = 20.680（2）A, V = 5979.7（11）A3, Z = 8, C32Hl2AgN13O3, Mr = 734.42, Dc = 1.632 g/cm3, μ= 0.734 mm-1, F（000） = 2928, S = 1.023 and T= 293（2） K. The final R = 0.0659 and wR = 0.1927 for 2118 observed reflections with I 〉 2σ（I）, and R = 0.0801 and wR = 0.2196 for all data. The complex builds up a packing structure by π-π stacking interactions and shows a luminescent feature.展开更多
A new coordination polymer, {[Cd(OPY)(tdc)(HO)]·H2 O}n(OPY = 4,4?-(oxybis(4,1-phenylene))dipyridine, H2 tdc = thiophene-2,5-dicarboxylic acid), has been synthesized hydrothermally based on a V-shaped ligand OPY. ...A new coordination polymer, {[Cd(OPY)(tdc)(HO)]·H2 O}n(OPY = 4,4?-(oxybis(4,1-phenylene))dipyridine, H2 tdc = thiophene-2,5-dicarboxylic acid), has been synthesized hydrothermally based on a V-shaped ligand OPY. The structure was fully characterized by elemental analysis, FT-IR spectroscopy, and X-ray single-crystal diffraction analysis. In1, two OPY ligands and one water molecule acted as terminal ligands coordinating to Cdcation to form [Cd(OPY)HO]units, which are then linked by tdc2-ligands to generate a one-dimensional chain. Every two adjacent chains linked by extensive O–H···O hydrogen bonds constitute one-dimensional double-chains, and such chains are extended into two-dimensional layers via O–H···N hydrogen bonds. These layers are further connected to form a three-dimensional supramolecular architecture via π-π stacking interactions. In addition, the thermal stability and solid state fluorescence property of 1 were also investigated.展开更多
The intramolecular aromatic-ring stacking interaction of mixed- ligand complex Pd(A)(UTP)^(2-)in the system pd^(2+)-A-UTP^(4-)has been determined by ~1HNMR,where A=1,10-phenanthroline(phen),2,2'-bipyridyl(bpy)and ...The intramolecular aromatic-ring stacking interaction of mixed- ligand complex Pd(A)(UTP)^(2-)in the system pd^(2+)-A-UTP^(4-)has been determined by ~1HNMR,where A=1,10-phenanthroline(phen),2,2'-bipyridyl(bpy)and DL- tryptophan(trp^-);UTP^(4-)=uridine 5-triphosphate.The result indicates that it is the partial stacking between the uracil ring of UTP^(4-)and the heterocyclic ring of A that makes H(5),H(6)and H(1')in the UTP^(4-)shift upfield signifi- cantly.Accordingly,the order of aromatic-ring interaction in the mixed- ligand complex has been obtained as follows:Pd(phen)(UTP)^(2-)(?)Pd(bpy)(UTP)^(2-) Pd(trp)(UTP)^(3-).展开更多
The stabilities of the complexes of three pyridine-like ligands with M(II)(ATP)^(2-) and M(II)(M=Ni,Co)were studied by spectrophotometry and by comparing the stability constants of the ternary complexes with these of ...The stabilities of the complexes of three pyridine-like ligands with M(II)(ATP)^(2-) and M(II)(M=Ni,Co)were studied by spectrophotometry and by comparing the stability constants of the ternary complexes with these of the binary complexes.A stacking interaction between the pyridine ring and the purine ring of ATP is indicated.The general existence of the stacking interaction encourages us to interpret the antitumor mechanism of a new class of antitumor drugs.展开更多
Non covalent interactions are quite common in all kinds of π-systems, such as π-π interactions, long range/short range van der waal force of interactions, ion-π interactions etc. Ab initio calculations are well es...Non covalent interactions are quite common in all kinds of π-systems, such as π-π interactions, long range/short range van der waal force of interactions, ion-π interactions etc. Ab initio calculations are well established and account well for the experimental long range interaction energies for small clusters of aromatic molecules and most of the calculations were carried out using the MPn methods. If a reasonably large basis set is used to calculate the stacking interaction energies for a cluster (dimer, trimer etc.) of aromatic molecules then the electron-electron correlation energy may be properly calculated. Moreover, ab initio calculations for aromatic π-systems show that the calculated stacking interaction energies highly depend on the basis set used and the electron correlation energy. In this investigation, the electron correlation of the stacked hydrated phenol systems has been accounted at MP2 level of calculations. We have calculated the π-π stacking interaction energies of the hydrated phenolic systems with different conformations.展开更多
Aromatic systems like phenol, diphenol, cyano benzene, chloro benzene, aniline etc shows effective π-π stacking interactions, long range van der Waals forces;ion-π interactions etc. and these forces of interactions...Aromatic systems like phenol, diphenol, cyano benzene, chloro benzene, aniline etc shows effective π-π stacking interactions, long range van der Waals forces;ion-π interactions etc. and these forces of interactions play an crucial role in the stability of stacked π-dimeric system. On the other hand, substituents and conformational change in the stacked dimmers of aromatic system may also change the stability of different stacked dimers. In this current study, stacked phenolic dimmers (both phenol and diphenol) have been taken for investigation of the stacking π-π interaction. But, the stacking interactions are also greatly affected by the conformational change with internal rotation (i.e. dihedral angle, φ) between the stacked dimers. It is generally accepted that larger basis sets are required for the highly accurate calculation of interaction energies for any stacked aromatic models. But, it has recently been reported that M062X/6-311++G(d,p) basis set is effectively better than that of B3LYP/6-311++G(d,p) for determining the interaction energies for any kind of long range interaction in aromatic systems. Therefore, all the calculations were carried out by using M062X/6-311++G(d,p) basis set. However, in most of the cases the calculated π-π stacking interaction energies show almost same result for both DFT and ab initio methods.展开更多
As the most abundant renewable aromatic biopolymer resource on the Earth,lignin has become a cutting-edge research hotspot in clean photocatalysis,thanks to the distinct highest occupied molecular-orbital and lowest u...As the most abundant renewable aromatic biopolymer resource on the Earth,lignin has become a cutting-edge research hotspot in clean photocatalysis,thanks to the distinct highest occupied molecular-orbital and lowest unoccupied molecular-orbital energy levels driven by the major β-O-4 linked bonds.However,the complex spatial architecture of functional groups,represented by benzene rings in the 3D intertwined macromolecular chains of lignin,and the challenge of enhancing carrier separation efficiency remain persistent obstacles hindering the development of lignin-based photocatalysts.Herein,a strategy of constructing lignin nanosphere-graphene oxide heterointerfaces(EL-GO)is proposed to comprehensively enhance the efficacy of functional groups and facilitate photoelectron migration modes.The recombination time of lightexcited photoelectrons is effectively prolonged by the π-π interactions between the“Donor site”and“Acceptor site”functional regions,along with the directional migration of photoelectrons between EL and GO.The photocatalytic efficiency of H_(2)O_(2) production using EL-GO is significantly enhanced under the protective mechanism of GO.To assess its potential,a prospect estimation of EL-GO in a lake containing various pollutants and metal ions was conducted,simulating real water conditions.This pioneering engineering effort aims to curb excessive consumption of fossil fuels and explore the green applications of lignin,thereby constructing a“carbon-neutral”feedstock system.展开更多
A comprehensive understanding of the relevance between molecular structure and passivation ability to screen efficient modifiers is essential for enhancing the performance of perovskite solar cells(PSCs).Here,three si...A comprehensive understanding of the relevance between molecular structure and passivation ability to screen efficient modifiers is essential for enhancing the performance of perovskite solar cells(PSCs).Here,three similarπ-πstacking molecules namely benzophenone(BPN),diphenyl sulfone(DPS),and diphenyl sulfoxide(DPSO)are used as back-interface modifiers in carbon-based CsPbBr_(3)PSCs.After investigation,the results demonstrate the positive effect of the p-πconjugation characteristic inπ-πstacking molecules on maximizing their passivation ability.The p-πco njugation of DPSO enables a higher coordinative activity of oxygen atom in its S=O group than that in 0=S=O group of DPS and C=O group of BPN,which gives a superior passivation effect of DPSO on defects of perovskite films.The modification of DPSO also significantly improves the p-type behavior of perovskite films and the back-interfacial energetics matching,inducing an increase of hole extraction and a decrease of energy loss.Finally,the unencapsulated carbon-based CsPbBr_(3)PSCs with DPSO achieve a maximum power conversion efficiency of 10.60%and outstanding long-term stability in high-temperature,high-humidity(85℃,85%relative humidity)air environment.This work provides insights into the influence of the structure ofπ-πstacking molecules on their ability to improve the perovskite films quality and therefore the PSCs performance.展开更多
Nuclear magnetic resonance(NMR)serves as a powerful tool for studying both the structure and dynamics of proteins.The NOE method,alongside residual dipolar;coupling,paramagnetic effects,J-coupling,and other related te...Nuclear magnetic resonance(NMR)serves as a powerful tool for studying both the structure and dynamics of proteins.The NOE method,alongside residual dipolar;coupling,paramagnetic effects,J-coupling,and other related techniques,has reached a level of maturity that allows for the determination of protein structures.Furthermore,NMR relaxation methods prove to be highly effective in characterizing protein dynamics across various timescales.The properties of protein systems are dictated by intra-and intermo-lecular interactions among atoms,which involve covalent bonds,hydrogen bonds(H-bonds),electrostatic interactions,and van der Waals forces.Multiple NMR approaches have been developed to measure noncovalent interactions,and this paper offers a concise overview of noncovalent interaction measurements using NMR,with a specific emphasis on the advancements accomplished in our laboratory.展开更多
Photocatalysis is one of the most capable green energy techniques for sustainable solar-to-chemical energy conversion.However,the speedy recombination of photocarriers remains a critical bottleneck in achieving high p...Photocatalysis is one of the most capable green energy techniques for sustainable solar-to-chemical energy conversion.However,the speedy recombination of photocarriers remains a critical bottleneck in achieving high photocatalytic efficiency.Recent advancements have underscored the pivotal role of internal and external electrostatic fields in regulating charge dynamics within semiconductor systems.This review highlights the emerging strategy of employing non-covalent electrostatic interactions to modulate photocatalytic behavior.Internally,spontaneous polarization within polar or ferroelectric semiconductors facilitates efficient charge separation through built-in electric fields.Externally applied mechanical stress and magnetic fields further augment these effects via piezoelectric and magnetoelectric phenomena,offering dynamic control over carrier transport.Beyond macroscopic fields,subtle non-covalent electrostatic forces,such as hydrogen bonds,van der Waals forces,andπ-πstacking,significantly influence surface adsorption,electronic structure modulation,and interfacial charge transfer processes.Combining these external influences with semiconductor properties,we can develop innovative strategies to stabilize the reactive intermediates and reduce the recombination pathways,improving the practical implications of these synergistic effects in energy conversion and environmental remediation.This review systematically elucidates the mechanistic contributions of internal polarization and external fields to the modulation of non-covalent electrostatic forces in photocatalytic systems.Emphasis is placed on material design strategies that integrate structural polarity,field-responsive behavior,and interfacial engineering to achieve superior photocatalytic performance.Finally,the prospects of non-covalent electrostatic interactions in photocatalysis are discussed,providing insights to guide the rational development of more efficient and sustainable photocatalytic systems.展开更多
The efficiency of organic semiconductor photocatalysts is typically limited by their capability of photogenerated electron transport.Herein,a photocatalyst is proposed initially through the specific axial coordination...The efficiency of organic semiconductor photocatalysts is typically limited by their capability of photogenerated electron transport.Herein,a photocatalyst is proposed initially through the specific axial coordination interaction between imidazole-C_(60)(ImC_(60))and zinc tetraphenyl porphyrin(ZnTPP)named ImC_(60)-ZnTPP.Subsequently,detailed structural characterizations along with theoretical calculation reveal that the unique ImC_(60)-ZnTPP possesses head-to-tail stacking supra-structures,leading to the formation of a continuous array of C_(60)–C_(60) with ultrashort spacing and ensuring strongπ–πinteractions and homogeneous electronic coupling,which could tremendously promote electron transport along the(−111)crystal facet of ImC_(60)-ZnTPP.Consequently,compared to other fullerene-based photocatalysts,ImC_(60)-ZnTPP shows exceptional photocatalytic hydrogen production activity,with an efficiency of up to 80.95 mmol g^(-1) h^(-1).This study provides a novel strategy to design highly efficient fullerene-based photocatalytic systems for solar-driven energy conversion and extend their artificial photosynthetic use.展开更多
Bioactive compounds could form aggregates that influence the bio-interactive processes. In this letter, based on π-π stacking models, quantitative aggregation-activity relationship （QAAR） studies were carried out ...Bioactive compounds could form aggregates that influence the bio-interactive processes. In this letter, based on π-π stacking models, quantitative aggregation-activity relationship （QAAR） studies were carried out on a series of sulfonylurea herbicides with good solubility. Four QAAR/QSAR models were constructed, which indicated that the bioactivity may strongly depend on both the characters of the dimeric aggregates and the monomer, The QAAR approach based on dimer-aggregates was also applicable for the highly water-soluble sulfonylurea herbicides that can form π-π stacking interactions. It was expected that the QAAR studies based on molecular aggregation state would be applied to other pesticide systems.展开更多
A series of“half-sandwich”bis(imino)pyridyl iron complexes with a substituted 8-(p-Xphenyl)naphthylamine(X=OMe,Me,CF3)was designed and synthesized by combining weakπ-πinteraction with steric and electronic tunings...A series of“half-sandwich”bis(imino)pyridyl iron complexes with a substituted 8-(p-Xphenyl)naphthylamine(X=OMe,Me,CF3)was designed and synthesized by combining weakπ-πinteraction with steric and electronic tunings.The weak noncovalentπ-πinteraction as well as the steric and electronic effects of bis(imino)pyridyl iron complexes were identified by experimental analyses and calculations.The roles of weakπ-πinteraction,steric bulk,and electronic tuning on the ethylene polymerization performance of bis(imino)pyridyl iron catalysts were studied in detail.The combination ofπ-πinteraction with steric and electronic tunings can access to thermally stable bis(imino)pyridyl iron at 130°C.展开更多
o understand the driving forces leading to mixed-ligand complexes in biologi-cal systenis.ternary complexes of M (ATP(L￣(2-) type, where M = Cu￣(2+), Ni￣(2+) orCo￣(2+) , and L= pyridine(Py) , 4-picoline, 3, 5-lut...o understand the driving forces leading to mixed-ligand complexes in biologi-cal systenis.ternary complexes of M (ATP(L￣(2-) type, where M = Cu￣(2+), Ni￣(2+) orCo￣(2+) , and L= pyridine(Py) , 4-picoline, 3, 5-lutidine, isoquinoline (lq) or benzimi-dazole(Bi) in aqueous solution were studied by spectropliotometry, some of them(M=Cu￣(2+), L = isoquinoline or benzimidazole) were also separately studied hy po-tentiometric pH titration. The results show that an intramolecular stacking interac-tion exists between the heteroaromatic ring of the ligands and the purine moiety ofATP.展开更多
An energetic salt, sodium nitroformate （NaNF）, was synthesized and characterized by elemental analysis, IR and UV spectra, and its crystal structure was first determined by single crystal X-ray diffraction. The stru...An energetic salt, sodium nitroformate （NaNF）, was synthesized and characterized by elemental analysis, IR and UV spectra, and its crystal structure was first determined by single crystal X-ray diffraction. The structure exhibits two types of π-π stacking interactions between the nitroformate anions, i e, the parallel-displaced and T-shaped confgurafions. Furthermore, the thermal decomposition mechanism was investigated by DSC, TG-DTG and FTIR techniques. The kinetic parameters of the thermal decomposition were also calculated by using Kissinger＇s and Ozawa-Doyle＇s methods. The results show that NaNF has a good thermal stability, which is attributed to the π-π stacking interactions.展开更多
The stacking of phenanthroline(phen) ligand within base pair sequences is one of the important factors for the stabilization of metalphen complex within DNA. The stacking ability of this ligand has been assessed to de...The stacking of phenanthroline(phen) ligand within base pair sequences is one of the important factors for the stabilization of metalphen complex within DNA. The stacking ability of this ligand has been assessed to deduce the base pair selectivity as well as to identify the favored region of intercalation. Different level of theories have been used to predict the favorable regions for stacking interaction of phen ligand with base pair, but the results of MP2/6-31+G(d,p) is found to be reasonably good for monitoring such interactions.展开更多
π-π Stacking in the 2,4,6-tris（4-pyridyl）-1,3,5-triazine aromatic nitrogen-containing ligand and its metal-ligand complex Zn（TPT）2（H2O）4（OH）2 1 has been investigated by single-crystal X-ray diffraction analy...π-π Stacking in the 2,4,6-tris（4-pyridyl）-1,3,5-triazine aromatic nitrogen-containing ligand and its metal-ligand complex Zn（TPT）2（H2O）4（OH）2 1 has been investigated by single-crystal X-ray diffraction analyses. The stacking mode of the ligand changes from the offset conformation to a perfect face-to-face alignment with the coordination to the zinc centers. The structure features are correlated with their solid-state luminescence properties. With excitation at 360 nm, free TPT ligand gives a strong fluorescent emission at 455 nm and the ligand-centered emission of the metal-ligand complex occurs at the same wavelength with lower emission intensity. The distance between the aromatic rings responds to the difference of luminescence characters.展开更多
基金supported by the National Natural Science Foundation of China (21577132)the Fundamental Research Funds for the Central Universities (2652015225)+1 种基金National High Technology Research and Development Program of China (2012AA062701)Students Innovation and Entrepreneurship Training Program 2015 of China University of Geosciences (201511415069),Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes~~
文摘A one-pot method for the preparation of g-C3N4/reduced graphene oxide（rGO） composite photocatalysts with controllable band structures is presented.The photocatalysts are characterized by Fouirer transform infrared spectroscopy,X-ray diffraction,scanning electron microscope,transmission electron microscope,and Mott-Schottky analysis.The valance band（VB） of g-C3N4 exhibits a noticeable positive shift upon hybridizing with rGO,and thus results in a strong photo-oxidation ability.The g-C3N4/rGO composites show a higher photodegradation activity for 2,4-dichlorophenol（2,4-DCP） and rhodamine B（RhB） under visible light irradiation（λ≥420 ran）.The g-C3N4/rGO-1sample exhibits the highest photocatalytic activity,which is 1.49 and 1.52 times higher than that of bulk g-C3N4 for 2,4-DCP and 1.52 times degradation,respectively.The enhanced photocatalytic activity for g-C3N4 originates from the improved visible light usage,enhanced electronic conductivity and photo-oxidation ability by the formed strong π-π stacking interactions with rGO.
基金support from the National Key R&D Program of China(grant number 2018YFA0702400)the Major Scientific and Technological Projects of CNPC(grant number ZD2019-183-007)the China Postdoctoral Science Foundation(grant number 2021M702041)。
文摘Unconsolidated sandstone reservoirs are most susceptible to sand production that leads to a dramatic oil production decline.In this study,the poly(4-vinyl pyridine)(P_(4)VP)incorporated with self-aggregating behavior was proposed for sand migration control.The P_(4)VP could aggregate sand grains spontaneously throughπ-πstacking interactions to withstand the drag forces sufficiently.The influential factors on the self-aggregating behavior of the P_(4)VP were evaluated by adhesion force test.The adsorption as well as desorption behavior of P_(4)VP on sand grains was characterized by scanning electron microscopy and adhesion force test at different pH conditions.The result indicated that the pH altered the forms of surface silanol groups on sand grains,which in turn affected the adsorption process of P_(4)VP.The spontaneous dimerization of P_(4)VP molecules resulting from theπ-πstacking interaction was demonstrated by reduced density gradient analysis,which contributed to the self-aggregating behavior and the thermally reversible characteristic of the P_(4)VP.Dynamic sand stabilization test revealed that the P_(4)VP showed wide pH and temperature ranges of application.The production of sands can be mitigated effectively at 20-130℃ within the pH range of 4-8.
基金supported by NNSFC (20701037)a Key Project from the CAS (KJCX2-YW-H01)the NSF of Fujian Province (E0510029)
文摘The reaction of 6,7-dicyanodipyridoquinoxaline （DICNQ） with AgNO3 in a 1：1 molar ratio by solution method gave a new complex [Ag（DICNQ）2]NO3 1. Single-crystal X-ray diffraction analysis reveals that the complex crystallizes in the space group Ibca of orthorhombic system with eight formula units in a cell. Crystal data for 1： a = 15.7055（17）, b = 18.411（2）, c = 20.680（2）A, V = 5979.7（11）A3, Z = 8, C32Hl2AgN13O3, Mr = 734.42, Dc = 1.632 g/cm3, μ= 0.734 mm-1, F（000） = 2928, S = 1.023 and T= 293（2） K. The final R = 0.0659 and wR = 0.1927 for 2118 observed reflections with I 〉 2σ（I）, and R = 0.0801 and wR = 0.2196 for all data. The complex builds up a packing structure by π-π stacking interactions and shows a luminescent feature.
基金Supported by the National Natural Science Foundation of China(Nos.21361023 and 21461023)
文摘A new coordination polymer, {[Cd(OPY)(tdc)(HO)]·H2 O}n(OPY = 4,4?-(oxybis(4,1-phenylene))dipyridine, H2 tdc = thiophene-2,5-dicarboxylic acid), has been synthesized hydrothermally based on a V-shaped ligand OPY. The structure was fully characterized by elemental analysis, FT-IR spectroscopy, and X-ray single-crystal diffraction analysis. In1, two OPY ligands and one water molecule acted as terminal ligands coordinating to Cdcation to form [Cd(OPY)HO]units, which are then linked by tdc2-ligands to generate a one-dimensional chain. Every two adjacent chains linked by extensive O–H···O hydrogen bonds constitute one-dimensional double-chains, and such chains are extended into two-dimensional layers via O–H···N hydrogen bonds. These layers are further connected to form a three-dimensional supramolecular architecture via π-π stacking interactions. In addition, the thermal stability and solid state fluorescence property of 1 were also investigated.
文摘The intramolecular aromatic-ring stacking interaction of mixed- ligand complex Pd(A)(UTP)^(2-)in the system pd^(2+)-A-UTP^(4-)has been determined by ~1HNMR,where A=1,10-phenanthroline(phen),2,2'-bipyridyl(bpy)and DL- tryptophan(trp^-);UTP^(4-)=uridine 5-triphosphate.The result indicates that it is the partial stacking between the uracil ring of UTP^(4-)and the heterocyclic ring of A that makes H(5),H(6)and H(1')in the UTP^(4-)shift upfield signifi- cantly.Accordingly,the order of aromatic-ring interaction in the mixed- ligand complex has been obtained as follows:Pd(phen)(UTP)^(2-)(?)Pd(bpy)(UTP)^(2-) Pd(trp)(UTP)^(3-).
基金Supported by the National Natural Science Foundation of Chinathe Doctoral Program Foundation of Institution of High Education the Research Foundation of State Key Laboratory of Coordination Chemistry,Nanjing University.
文摘The stabilities of the complexes of three pyridine-like ligands with M(II)(ATP)^(2-) and M(II)(M=Ni,Co)were studied by spectrophotometry and by comparing the stability constants of the ternary complexes with these of the binary complexes.A stacking interaction between the pyridine ring and the purine ring of ATP is indicated.The general existence of the stacking interaction encourages us to interpret the antitumor mechanism of a new class of antitumor drugs.
文摘Non covalent interactions are quite common in all kinds of π-systems, such as π-π interactions, long range/short range van der waal force of interactions, ion-π interactions etc. Ab initio calculations are well established and account well for the experimental long range interaction energies for small clusters of aromatic molecules and most of the calculations were carried out using the MPn methods. If a reasonably large basis set is used to calculate the stacking interaction energies for a cluster (dimer, trimer etc.) of aromatic molecules then the electron-electron correlation energy may be properly calculated. Moreover, ab initio calculations for aromatic π-systems show that the calculated stacking interaction energies highly depend on the basis set used and the electron correlation energy. In this investigation, the electron correlation of the stacked hydrated phenol systems has been accounted at MP2 level of calculations. We have calculated the π-π stacking interaction energies of the hydrated phenolic systems with different conformations.
文摘Aromatic systems like phenol, diphenol, cyano benzene, chloro benzene, aniline etc shows effective π-π stacking interactions, long range van der Waals forces;ion-π interactions etc. and these forces of interactions play an crucial role in the stability of stacked π-dimeric system. On the other hand, substituents and conformational change in the stacked dimmers of aromatic system may also change the stability of different stacked dimers. In this current study, stacked phenolic dimmers (both phenol and diphenol) have been taken for investigation of the stacking π-π interaction. But, the stacking interactions are also greatly affected by the conformational change with internal rotation (i.e. dihedral angle, φ) between the stacked dimers. It is generally accepted that larger basis sets are required for the highly accurate calculation of interaction energies for any stacked aromatic models. But, it has recently been reported that M062X/6-311++G(d,p) basis set is effectively better than that of B3LYP/6-311++G(d,p) for determining the interaction energies for any kind of long range interaction in aromatic systems. Therefore, all the calculations were carried out by using M062X/6-311++G(d,p) basis set. However, in most of the cases the calculated π-π stacking interaction energies show almost same result for both DFT and ab initio methods.
基金National Natural Science Foundation of China,Grant/Award Numbers:22178037,22278046,U22A20424Liaoning Education Department Project,Grant/Award Number:JYTMS20230396。
文摘As the most abundant renewable aromatic biopolymer resource on the Earth,lignin has become a cutting-edge research hotspot in clean photocatalysis,thanks to the distinct highest occupied molecular-orbital and lowest unoccupied molecular-orbital energy levels driven by the major β-O-4 linked bonds.However,the complex spatial architecture of functional groups,represented by benzene rings in the 3D intertwined macromolecular chains of lignin,and the challenge of enhancing carrier separation efficiency remain persistent obstacles hindering the development of lignin-based photocatalysts.Herein,a strategy of constructing lignin nanosphere-graphene oxide heterointerfaces(EL-GO)is proposed to comprehensively enhance the efficacy of functional groups and facilitate photoelectron migration modes.The recombination time of lightexcited photoelectrons is effectively prolonged by the π-π interactions between the“Donor site”and“Acceptor site”functional regions,along with the directional migration of photoelectrons between EL and GO.The photocatalytic efficiency of H_(2)O_(2) production using EL-GO is significantly enhanced under the protective mechanism of GO.To assess its potential,a prospect estimation of EL-GO in a lake containing various pollutants and metal ions was conducted,simulating real water conditions.This pioneering engineering effort aims to curb excessive consumption of fossil fuels and explore the green applications of lignin,thereby constructing a“carbon-neutral”feedstock system.
基金financial supports from the Natural Science Foundation of Shandong Province(ZR2021ME037)the National Natural Science Foundation of China(52472259,22179051 and 61604143)+2 种基金the National Key Research and Development Program of China(2021YFE0111000)the Special Fund of Taishan Scholar Program of Shandong Province(tsqnz20221141)the Foundation of Key Laboratory of Advanced Technique&Preparation for Renewable Energy Materials,Ministry of Education,Yunnan Normal University(OF2022-02)。
文摘A comprehensive understanding of the relevance between molecular structure and passivation ability to screen efficient modifiers is essential for enhancing the performance of perovskite solar cells(PSCs).Here,three similarπ-πstacking molecules namely benzophenone(BPN),diphenyl sulfone(DPS),and diphenyl sulfoxide(DPSO)are used as back-interface modifiers in carbon-based CsPbBr_(3)PSCs.After investigation,the results demonstrate the positive effect of the p-πconjugation characteristic inπ-πstacking molecules on maximizing their passivation ability.The p-πco njugation of DPSO enables a higher coordinative activity of oxygen atom in its S=O group than that in 0=S=O group of DPS and C=O group of BPN,which gives a superior passivation effect of DPSO on defects of perovskite films.The modification of DPSO also significantly improves the p-type behavior of perovskite films and the back-interfacial energetics matching,inducing an increase of hole extraction and a decrease of energy loss.Finally,the unencapsulated carbon-based CsPbBr_(3)PSCs with DPSO achieve a maximum power conversion efficiency of 10.60%and outstanding long-term stability in high-temperature,high-humidity(85℃,85%relative humidity)air environment.This work provides insights into the influence of the structure ofπ-πstacking molecules on their ability to improve the perovskite films quality and therefore the PSCs performance.
文摘Nuclear magnetic resonance(NMR)serves as a powerful tool for studying both the structure and dynamics of proteins.The NOE method,alongside residual dipolar;coupling,paramagnetic effects,J-coupling,and other related techniques,has reached a level of maturity that allows for the determination of protein structures.Furthermore,NMR relaxation methods prove to be highly effective in characterizing protein dynamics across various timescales.The properties of protein systems are dictated by intra-and intermo-lecular interactions among atoms,which involve covalent bonds,hydrogen bonds(H-bonds),electrostatic interactions,and van der Waals forces.Multiple NMR approaches have been developed to measure noncovalent interactions,and this paper offers a concise overview of noncovalent interaction measurements using NMR,with a specific emphasis on the advancements accomplished in our laboratory.
基金the Deputyship for Research and Innovation,“Ministry of Education”in Saudi Arabia for funding this research(IFKSU-HCRA-12-3).
文摘Photocatalysis is one of the most capable green energy techniques for sustainable solar-to-chemical energy conversion.However,the speedy recombination of photocarriers remains a critical bottleneck in achieving high photocatalytic efficiency.Recent advancements have underscored the pivotal role of internal and external electrostatic fields in regulating charge dynamics within semiconductor systems.This review highlights the emerging strategy of employing non-covalent electrostatic interactions to modulate photocatalytic behavior.Internally,spontaneous polarization within polar or ferroelectric semiconductors facilitates efficient charge separation through built-in electric fields.Externally applied mechanical stress and magnetic fields further augment these effects via piezoelectric and magnetoelectric phenomena,offering dynamic control over carrier transport.Beyond macroscopic fields,subtle non-covalent electrostatic forces,such as hydrogen bonds,van der Waals forces,andπ-πstacking,significantly influence surface adsorption,electronic structure modulation,and interfacial charge transfer processes.Combining these external influences with semiconductor properties,we can develop innovative strategies to stabilize the reactive intermediates and reduce the recombination pathways,improving the practical implications of these synergistic effects in energy conversion and environmental remediation.This review systematically elucidates the mechanistic contributions of internal polarization and external fields to the modulation of non-covalent electrostatic forces in photocatalytic systems.Emphasis is placed on material design strategies that integrate structural polarity,field-responsive behavior,and interfacial engineering to achieve superior photocatalytic performance.Finally,the prospects of non-covalent electrostatic interactions in photocatalysis are discussed,providing insights to guide the rational development of more efficient and sustainable photocatalytic systems.
基金supported by the National Natural Science Foundation of China(52322204,52072374,52272052)the National Key R&D Program of China(Grant No.2022YFA1205900)the Youth Innovation Promotion Association of CAS(Y2022015).
文摘The efficiency of organic semiconductor photocatalysts is typically limited by their capability of photogenerated electron transport.Herein,a photocatalyst is proposed initially through the specific axial coordination interaction between imidazole-C_(60)(ImC_(60))and zinc tetraphenyl porphyrin(ZnTPP)named ImC_(60)-ZnTPP.Subsequently,detailed structural characterizations along with theoretical calculation reveal that the unique ImC_(60)-ZnTPP possesses head-to-tail stacking supra-structures,leading to the formation of a continuous array of C_(60)–C_(60) with ultrashort spacing and ensuring strongπ–πinteractions and homogeneous electronic coupling,which could tremendously promote electron transport along the(−111)crystal facet of ImC_(60)-ZnTPP.Consequently,compared to other fullerene-based photocatalysts,ImC_(60)-ZnTPP shows exceptional photocatalytic hydrogen production activity,with an efficiency of up to 80.95 mmol g^(-1) h^(-1).This study provides a novel strategy to design highly efficient fullerene-based photocatalytic systems for solar-driven energy conversion and extend their artificial photosynthetic use.
基金National Key Technology R&D Program of China(No.2011BAE06B05)National Natural Science Foundation of China(No.21172070)+2 种基金National High Technology Research Development Program of China(No.2011AA10A207)National Basic Research Program of China(No.2010CB126100)the Fundamental Research Funds for the Central Universities
文摘Bioactive compounds could form aggregates that influence the bio-interactive processes. In this letter, based on π-π stacking models, quantitative aggregation-activity relationship （QAAR） studies were carried out on a series of sulfonylurea herbicides with good solubility. Four QAAR/QSAR models were constructed, which indicated that the bioactivity may strongly depend on both the characters of the dimeric aggregates and the monomer, The QAAR approach based on dimer-aggregates was also applicable for the highly water-soluble sulfonylurea herbicides that can form π-π stacking interactions. It was expected that the QAAR studies based on molecular aggregation state would be applied to other pesticide systems.
基金supported by the State Key Research Development Program of China(No.2021YFB3800701)National Natural Science Foundation of China(NSFC,No.52173016)+2 种基金Guangdong Basic and Applied Basic Research Foundation(Nos.2024A1515012784,2024A1515011102,and 2023A1515110549)Fundamental Research Funds for the Central Universities,Sun Yat-sen University(No.24qnpy047)PetroChina Scientific and Technological Projects(No.2022DJ6308).
文摘A series of“half-sandwich”bis(imino)pyridyl iron complexes with a substituted 8-(p-Xphenyl)naphthylamine(X=OMe,Me,CF3)was designed and synthesized by combining weakπ-πinteraction with steric and electronic tunings.The weak noncovalentπ-πinteraction as well as the steric and electronic effects of bis(imino)pyridyl iron complexes were identified by experimental analyses and calculations.The roles of weakπ-πinteraction,steric bulk,and electronic tuning on the ethylene polymerization performance of bis(imino)pyridyl iron catalysts were studied in detail.The combination ofπ-πinteraction with steric and electronic tunings can access to thermally stable bis(imino)pyridyl iron at 130°C.
文摘o understand the driving forces leading to mixed-ligand complexes in biologi-cal systenis.ternary complexes of M (ATP(L￣(2-) type, where M = Cu￣(2+), Ni￣(2+) orCo￣(2+) , and L= pyridine(Py) , 4-picoline, 3, 5-lutidine, isoquinoline (lq) or benzimi-dazole(Bi) in aqueous solution were studied by spectropliotometry, some of them(M=Cu￣(2+), L = isoquinoline or benzimidazole) were also separately studied hy po-tentiometric pH titration. The results show that an intramolecular stacking interac-tion exists between the heteroaromatic ring of the ligands and the purine moiety ofATP.
基金Funded by the National"973"Projectthe National Natural Science Foundation of China(No.20471008)+1 种基金the Natural Science Foundation of Chongqing(No.cstc2011jjA50013)the Chongqing Municipal Commission of Education(No.KJ111310)
文摘An energetic salt, sodium nitroformate （NaNF）, was synthesized and characterized by elemental analysis, IR and UV spectra, and its crystal structure was first determined by single crystal X-ray diffraction. The structure exhibits two types of π-π stacking interactions between the nitroformate anions, i e, the parallel-displaced and T-shaped confgurafions. Furthermore, the thermal decomposition mechanism was investigated by DSC, TG-DTG and FTIR techniques. The kinetic parameters of the thermal decomposition were also calculated by using Kissinger＇s and Ozawa-Doyle＇s methods. The results show that NaNF has a good thermal stability, which is attributed to the π-π stacking interactions.
文摘The stacking of phenanthroline(phen) ligand within base pair sequences is one of the important factors for the stabilization of metalphen complex within DNA. The stacking ability of this ligand has been assessed to deduce the base pair selectivity as well as to identify the favored region of intercalation. Different level of theories have been used to predict the favorable regions for stacking interaction of phen ligand with base pair, but the results of MP2/6-31+G(d,p) is found to be reasonably good for monitoring such interactions.
基金Financially supported by NNSFC (No. 20701014)NSFFPC (No. 2003 F006)the SRP Program of SCUT
文摘π-π Stacking in the 2,4,6-tris（4-pyridyl）-1,3,5-triazine aromatic nitrogen-containing ligand and its metal-ligand complex Zn（TPT）2（H2O）4（OH）2 1 has been investigated by single-crystal X-ray diffraction analyses. The stacking mode of the ligand changes from the offset conformation to a perfect face-to-face alignment with the coordination to the zinc centers. The structure features are correlated with their solid-state luminescence properties. With excitation at 360 nm, free TPT ligand gives a strong fluorescent emission at 455 nm and the ligand-centered emission of the metal-ligand complex occurs at the same wavelength with lower emission intensity. The distance between the aromatic rings responds to the difference of luminescence characters.
