Trimethoprim(TMP),as a broad-spectrum bacteriostatic antibiotic,is widely used in clinical anti-infection therapy and livestock breeding.However,its low water solubility leads to insufficient bioavailability,which has...Trimethoprim(TMP),as a broad-spectrum bacteriostatic antibiotic,is widely used in clinical anti-infection therapy and livestock breeding.However,its low water solubility leads to insufficient bioavailability,which has become a key problem restricting its development.Cyclodextrins and their derivatives,with their unique cyclic structures,can form inclusion complexes with TMP to improve its properties.This article reviews the pharmacological characteristics of TMP,the types and properties of common cyclodextrins,focusing on introducing various preparation methods of trimethoprim cyclodextrin inclusion complexes and multiple characterization methods for identifying the inclusion complexes,aiming to provide a reference for further research and development of trimethoprim cyclodextrin inclusion complexes.展开更多
To expand the study on the structures and biological activities of the anthracyclines anticancer drugs and reduce their toxic side effects,the new anthraquinone derivatives,9‑pyridylanthrahydrazone(9‑PAH)and 9,10‑bisp...To expand the study on the structures and biological activities of the anthracyclines anticancer drugs and reduce their toxic side effects,the new anthraquinone derivatives,9‑pyridylanthrahydrazone(9‑PAH)and 9,10‑bispyridylanthrahydrazone(9,10‑PAH)were designed and synthesized.Utilizing 9‑PAH and 9,10‑PAH as promising anticancer ligands,their respective copper complexes,namely[Cu(L1)Cl_(2)]Cl(1)and{[Cu_(4)(μ_(2)‑Cl)_(3)Cl_(4)(9,10‑PAH)_(2)(DMSO)_(2)]Cl_(2)}_(n)(2),were subsequently synthesized,where the new ligand L1 is formed by coupling two 9‑PAH ligands in the coordination reaction.The chemical and crystal structures of 1 and 2 were elucidated by IR,MS,elemental analysis,and single‑crystal X‑ray diffraction.Complex 1 forms a mononuclear structure.L1 coordinates with Cu through its three N atoms,together with two Cl atoms,to form a five‑coordinated square pyramidal geometry.Complex 2 constitutes a polymeric structure,wherein each structural unit centrosymmetrically encompasses two five‑coordinated binuclear copper complexes(Cu1,Cu2)of 9,10‑PAH,with similar square pyramidal geometry.A chlorine atom(Cl_(2)),located at the symmetry center,bridges Cu1 and Cu1A to connect the two binuclear copper structures.Meanwhile,the two five‑coordinated Cu2 atoms symmetrically bridge the adjacent structural units via one coordinated Cl atom,respectively,thus forming a 1D chain‑like polymeric structure.In vitro anticancer activity assessments revealed that 1 and 2 showed significant cytotoxicity even higher than cisplatin.Specifically,the IC_(50)values of 2 against HeLa‑229 and SK‑OV‑3 cancer cell lines were determined to be(5.92±0.32)μmol·L^(-1)and(6.48±0.39)μmol·L^(-1),respectively.2 could also block the proliferation of HeLa‑229 cells in S phase and significantly induce cell apoptosis.In addition,fluorescence quenching competition experiments suggested that 2 might interact with DNA by an intercalative binding mode,offering insights into its underlying anticancer mechanism.CCDC:2388918,1;2388919,2.展开更多
Parkinson's disease(PD)is a debilitating and progressive neurodegenerative disorder with complex pathology and multiple membrane barriers that hinder drug delivery,resulting in the absence of ideal therapeutic dru...Parkinson's disease(PD)is a debilitating and progressive neurodegenerative disorder with complex pathology and multiple membrane barriers that hinder drug delivery,resulting in the absence of ideal therapeutic drugs with minimal side effects[1].Recently,natural medicine has garnered significant attention due to its remarkable efficacy and limited side effects.Icariin,a naturally occurring flavonoid,exhibits excellent potential as a therapeutic agent for neurodegenerative disease[2].However,its clinical application is limited by poor water solubility,low bioavailability,and high clearance rates.Here,an aqueous formulation of icariin/hydroxypropyl-β-cyclodextrin(HP-β-CD)supramolecular inclusion complex was obtained to optimize icariin properties.Furthermore,icariin cyclodextrin supramolecular inclusion complex based thermosensitive(icariin gels)was innovated.At lower temperatures,it remained in a liquid phase with high fluidity.Upon reaching the gelation temperature,it underwent a transition to a gel phase with significantly reduced fluidity,which may be suitable for the design of an intranasal delivery system for PD treatment.The innovative approach capitalizes on the exceptional characteristics of HP-β-CD,which was utilized to synergize with nasal delivery for targeted brain delivery and with icariin for PD treatment[3,4].展开更多
The dissolution behavior of complex inclusions in refining slag was studied using confocal laser scanning microscope.Based on the dissolution curve of complex inclusions,the main rate-limiting link of CaO-SiO_(2)-Al_(...The dissolution behavior of complex inclusions in refining slag was studied using confocal laser scanning microscope.Based on the dissolution curve of complex inclusions,the main rate-limiting link of CaO-SiO_(2)-Al_(2)O_(3)complex inclusions was the diffusion in the molten slag.The dissolution rate of CaO-SiO_(2)-Al_(2)O_(3)complex inclusions was affected by the composition and size of inclusion.The functional relationship between the dimensionless inclusion capacity(Zh)and the dimensionless dissolution rate(Ry)of CaO-SiO_(2)-Al_(2)O_(3)complex inclusions was calculated as Ry=2.10×10^(-6)Zh^(0.160),while it was Ry=2.10×10^(-6)Zh^(0.0087)for Al_(2)O_(3)-CaO complex inclusions.On this basis,the complete dissolution time and rate of the complex inclusions were calculated by using the function relation between the Zh and Ry numbers.展开更多
The characteristics of nonmetallic inclusions formed during steel production have a significant influence on steel performance.In this paper,studies on inclusions using confocal scanning laser microscopy(CSLM)are revi...The characteristics of nonmetallic inclusions formed during steel production have a significant influence on steel performance.In this paper,studies on inclusions using confocal scanning laser microscopy(CSLM)are reviewed and summarized,particularly the col-lision of various inclusions,dissolution of inclusions in liquid slag,and reactions between inclusions and steel.Solid inclusions exhibited a high collision tendency,whereas pure liquid inclusions exhibited minimal collisions because of the small attraction force induced by their<90°contact angle with molten steel.The collision of complex inclusions in molten steel was not included in the scope of this study and should be evaluated in future studies.Higher CaO/Al_(2)O_(3)and CaO/SiO_(2)ratios in liquid slag promoted the dissolution of Al_(2)O_(3)-based in-clusions.The formation of solid phases in the slag should be prevented to improve dissolution of inclusions.To accurately simulate the dissolution of inclusions in liquid slag,in-situ observation of the dissolution of inclusions at the steel-slag interface is necessary.Using a combination of CSLM and scanning electron microscopy-energy dispersive spectroscopy,the composition and morphological evolution of the inclusions during their modification by the dissolved elements in steel were observed and analyzed.Although the in-situ observa-tion of MnS and TiN precipitations has been widely studied,the in-situ observation of the evolution of oxide inclusions in steel during so-lidification and heating processes has rarely been reported.The effects of temperature,heating and cooling rates,and inclusion character-istics on the formation of acicular ferrites(AFs)have been widely studied.At a cooling rate of 3-5 K/s,the order of AF growth rate in-duced by different inclusions,as reported in literature,is Ti-O<Ti-Ca-Zr-Al-O<Mg-O<Ti-Zr-Al-O<Mn-Ti-Al-O<Ti-Al-O<Zr-Ti-Al-O.Further comprehensive experiments are required to investigate the quantitative relationship between the formation of AFs and inclusions.展开更多
Rare earth La was introduced into 40Cr steel in industrial experiments to achieve the purpose of modifying inclusions.The impact of La on the inclusion modification was studied,and its influence on the solidification ...Rare earth La was introduced into 40Cr steel in industrial experiments to achieve the purpose of modifying inclusions.The impact of La on the inclusion modification was studied,and its influence on the solidification structure was further investigated.With adding 0.0023%La,the Al_(2)O_(3)·CaO·CaS inclusions were modified to the LaAlO_(3)·CaO·CaS inclusions.Additionally,the morphology tended to be more spherical,and the proportion of small-sized inclusions increased significantly from 77.8%to 93.5%.The large-sized inclusions were almost completely eliminated.Based on experimental results,a dynamical model elucidating the process of inclusion modification by La was developed.Furthermore,the ratio of equiaxed zone of the solidification structure increased from 22.9%to 31.0%,and the average primary dendrite arm spacing decreased significantly from 288.4 to 226.2μm.Two-dimensional lattice mismatch analysis results determined that LaAlO_(3)can serve as an effective heterogeneous nucleation core,leading to solidification structure refinement.The beneficial transformation of inclusions and refinement of solidification structure are conducive to the cold heading process of 40Cr steel.展开更多
The transformation mechanism of the inclusions and microstructure in 316L stainless steel after post-isothermal heat treatment(IHT)was revealed,along with the pitting behavior of the inclusions in a chloride environme...The transformation mechanism of the inclusions and microstructure in 316L stainless steel after post-isothermal heat treatment(IHT)was revealed,along with the pitting behavior of the inclusions in a chloride environment before and after the transformation.The effect of the inclusion transformation on the pitting corrosion behavior of 316L stainless steel and its intrinsic mechanism was also revealed.Results revealed a gradual transformation of MnO-SiO_(2)inclusions into MnO-Cr_(2)O_(3) within the temperature range of 1373 to 1573 K.MnO-Cr_(2)O_(3)inclusions exhibited minimal dissolution in chloride ion corrosion environments,while MnO-SiO_(2)oxides demonstrated higher electrochemical activity and were more prone to dissolve and form pits.Meanwhile,IHT significantly reduced the dislocation density of stainless steel,rendering it more stable in corrosive environments.X-ray photoelectron spectroscopy peak distributions of the passive films demonstrated that IHT increased the proportion of Cr and Fe oxides and hydroxides in the passive film which improved the stability and corrosion resistance of the steel.展开更多
Metal complexes hold significant promise in tumor diagnosis and treatment.However,their potential applications in photodynamic therapy(PDT)are hindered by issues such as poor photostability,low yield of reactive oxyge...Metal complexes hold significant promise in tumor diagnosis and treatment.However,their potential applications in photodynamic therapy(PDT)are hindered by issues such as poor photostability,low yield of reactive oxygen species(ROS),and aggregation-induced ROS quenching.To address these challenges,we present a molecular self-assembly strategy utilizing aggregation-induced emission(AIE)conjugates for metal complexes.As a proof of concept,we synthesized a mitochondrial-targeting cyclometalated Ir(Ⅲ)photosensitizer Ir-TPE.This approach significantly enhances the photodynamic effect while mitigating the dark toxicity associated with AIE groups.Ir-TPE readily self-assembles into nanoaggregates in aqueous solution,leading to a significant production of ROS upon light irradiation.Photoirradiated Ir-TPE triggers multiple modes of death by excessively accumulating ROS in the mitochondria,resulting in mitochondrial DNA damage.This damage can lead to ferroptosis and autophagy,two forms of cell death that are highly cytotoxic to cancer cells.The aggregation-enhanced photodynamic effect of Ir-TPE significantly enhances the production of ROS,leading to a more pronounced cytotoxic effect.In vitro and in vivo experiments demonstrate this aggregation-enhanced PDT approach achieves effective in situ tumor eradication.This study not only addresses the limitations of metal complexes in terms of low ROS production due to aggregation but also highlights the potential of this strategy for enhancing ROS production in PDT.展开更多
The purpose of this article is to introduce a new method with a self-adaptive stepsize for approximating a common solution of monotone inclusion problems and variational inequality problems in reflexive Banach spaces....The purpose of this article is to introduce a new method with a self-adaptive stepsize for approximating a common solution of monotone inclusion problems and variational inequality problems in reflexive Banach spaces.The strong convergence result for our method is established under some standard assumptions without any requirement of the knowledge of the Lipschitz constant of the mapping.Several numerical experiments are provided to verify the advantages and efficiency of proposed algorithms.展开更多
Two novel lanthanide complexes,[Sm_(2)(BA)_(6)(4-OH-terpy)_(2)]·2H_(2)O·2EtOH(1)and[Pr_(2)(BA)_(6)(4-OH-terpy)_(2)(H_(2)O)_(2)]·HBA·H_(2)O(2),where HBA=benzoic acid,4-OH-terpy=4-hydroxy-2,2'∶6...Two novel lanthanide complexes,[Sm_(2)(BA)_(6)(4-OH-terpy)_(2)]·2H_(2)O·2EtOH(1)and[Pr_(2)(BA)_(6)(4-OH-terpy)_(2)(H_(2)O)_(2)]·HBA·H_(2)O(2),where HBA=benzoic acid,4-OH-terpy=4-hydroxy-2,2'∶6',2″-terpyridine,were successfully synthesized using ultrasonic dissolution and the conventional solution method with two mixed ligands HBA and 4-OH-terpy.During the synthesis,4-OH-terpy was involved in the reaction as a neutral ligand,while HBA,in its deprotonated form(BA-),coordinated with the lanthanide ions as an acidic ligand.The crystal structures of these two complexes were precisely determined by single-crystal X-ray diffraction.Elemental analysis,infrared and Raman spectroscopy,and powder X-ray diffraction techniques were also employed to further explore the physicochemical properties of the two complexes.The single-crystal X-ray diffraction data indicate that,despite their structural differences,both complexes belong to the triclinic crystal system P1 space group.The central lanthanide ions have the same coordination number but exhibit different coordination environments.To comprehensively evaluate the thermal stability of these two complexes,comprehensive tests including thermogravimetric analysis,differential thermogravimetric analysis,differential scanning calorimetry,Fourier transform infrared spectroscopy,and mass spectrometry were conducted.Meanwhile,an in-depth investigation was conducted into the 3D infrared stacked images and mass spectra of the gases emitted from the complexes.In addition,studies of the fluorescence properties of complex1 showed that it exhibited fluorescence emission matching the Sm^(3+)characteristic transition.展开更多
To extend a new family of aminophosphine-coordinated[FeFe]-hydrogenase mimics for catalytic hydro-gen(H_(2))evolution,we carried out the ligand substitutions of diiron hexacarbonyl precursors[Fe_(2)(μ-X_(2)pdt)(CO)_(...To extend a new family of aminophosphine-coordinated[FeFe]-hydrogenase mimics for catalytic hydro-gen(H_(2))evolution,we carried out the ligand substitutions of diiron hexacarbonyl precursors[Fe_(2)(μ-X_(2)pdt)(CO)_(6)](X_(2)pdt=(SCH_(2))_(2)CX_(2),X=Me,H)with aminodiphosphines(Ph_(2)PCH_(2))_(2)NY(Y=(CH_(2))_(2)OH,(CH_(2))_(3)OH)to obtain two new diiron aminophosphine complexes[Fe_(2)(L1)(μ-Me_(2)pdt)(CO)_(5)](1)and[Fe_(2)(L2)(μ-H_(2)pdt)(CO)_(5)](2),where L1=3-[(diphe-nylphosphaneyl)methyl]oxazolidine,L2=3-[(diphenylphosphaneyl)methyl]-1,3-oxazinane.Moreover,the structures of 1 and 2 have been fully confirmed by elemental analysis,spectroscopic techniques,and single-crystal X-ray diffraction.Using cyclic voltammetry(CV),we investigated the electrochemical redox performance and proton reduc-tion activities of 1 and 2 in acetic acid(HOAc).The CV study indicates that diiron aminophosphine complexes 1 and 2 can be considered to be hydrogenase-inspired diiron molecular electrocatalysts for the reduction of protons into H 2 generation in the presence of HOAc.CCDC:2443967,1;2443969,2.展开更多
In order to mitigate the harm of alumina,calcium aluminate,and magnesium aluminum spinel inclusions on the fatigue performance of bearing steel,the effect of Ce-Mg composite treatment on the cleanliness of silicon-kil...In order to mitigate the harm of alumina,calcium aluminate,and magnesium aluminum spinel inclusions on the fatigue performance of bearing steel,the effect of Ce-Mg composite treatment on the cleanliness of silicon-killed GCr15 bearing steel and the evolution of Ce-Mg-Mn-O-S composite inclusions during heat treatment of the steels at 1523 K were investigated in this present work.The results indicate that the cleanliness of S2 with 0.0045 wt%Ce and 0.0016 wt%Mg is better than that in S1 with0.0020 wt%Ce and 0.0011 wt%Mg,which is attributed to the more effective removal of Ce-Mg-Mn-O-S composite inclusions,with help of good aggregation capacity of Ce-containing inclusions and small volume density of Mg-containing inclusions,due to the increase of rare earth and magnesium content.The aspect ratio and area fraction of the Ce-Mg-Mn-O-S composite inclusions in as-cast steel decrease significantly with isothermal treatment at 1523 K for 150 min,due to the effect of(ⅰ)Ostwald aging mechanism of inclusions and(ⅱ)sulfide solid solution during isothermal treatment.With the increase of isothermal treatment time from 150 to 550 min,the aspect ratio and area fraction of the inclusions in SO(untreated steel)and S1 decrease slightly,because spheroidization and solid solution of inclusions reach their basic equilibrium at 1523 K.However,the aspect ratio and area fraction of the Ce-Mg-Mn-O-S composite inclusions in S2 actually increase,and the inclusions evolve into three-phase(two-phase)inclusions,which is attributed to(ⅲ)transformation of phase compositions in inclusions and interfacial reaction between inclusions and steel matrix during isothermal heating.Therefore,the control of inclusions in silicon-killed bearing steel with Ce and Mg composite treatment should be combined with specific heat treatment processes and appropriate rare earth and magnesium contents,to minimize the damage of inclusions on the fatigue performance of bearing steel products.展开更多
Two Gd_(2)complexes,namely[Gd_(2)(dbm)_(2)(HL_(1))_(2)(CH_(3)OH)_(2)]·4CH_(3)OH(1)and[Gd_(2)(dbm)_(2)(L_(2))_(2)(CH_(3)OH)_(2)]·2CH_(3)OH(2),where H_(3)L_(1)=(Z)-N'-[4-(diethylamino)-2-hydroxybenzylidene...Two Gd_(2)complexes,namely[Gd_(2)(dbm)_(2)(HL_(1))_(2)(CH_(3)OH)_(2)]·4CH_(3)OH(1)and[Gd_(2)(dbm)_(2)(L_(2))_(2)(CH_(3)OH)_(2)]·2CH_(3)OH(2),where H_(3)L_(1)=(Z)-N'-[4-(diethylamino)-2-hydroxybenzylidene]-2-hydroxyacetohydrazide,H_(2)L_(2)=(E)-N'-(5-bromo-2-hydroxy-3-methoxybenzylidene)nicotinohydrazide,Hdbm=dibenzoylmethane,have been constructed by adopting the solvothermal method.Structural characterization unveils that both complexes 1 and 2 are constituted by two Gd^(3+)ions,two dbm-ions,two CH_(3)OH molecules,and two polydentate Schiff-base ligands(HL_(1)^(2-)or L_(2)^(2-)).In addition,complex 1 contains four free methanol molecules,whereas complex 2 harbors two free methanol molecules.By investigating the interactions between complexes 1 and 2 and four types of bacteria(Bacillus subtilis,Escherichia coli,Staphylococcus aureus,Candida albicans),it was found that both complexes 1 and 2 exhibited potent antibacte-rial activities.The interaction mechanisms between the ligands H_(3)L_(1),H_(2)L_(2),complexes 1 and 2,and calf thymus DNA(CT-DNA)were studied using ultraviolet-visible spectroscopy,fluorescence titration,and cyclic voltammetry.The results demonstrated that both complexes 1 and 2 can intercalate into CT-DNA molecules,thereby inhibiting bacterial proliferation to achieve the antibacterial effects.CCDC:2401116,1;2401117,2.展开更多
We have examined the theoretical implications of combining two main and three auxiliary ligands to form several Ir(Ⅲ)complexes featuring a transition metal as their core atom to identify some appropriate organic ligh...We have examined the theoretical implications of combining two main and three auxiliary ligands to form several Ir(Ⅲ)complexes featuring a transition metal as their core atom to identify some appropriate organic lightemitting diode(OLED)materials.By utilizing electronic structure,frontier molecular orbitals,minimum single-line absorption,triplet excited states,and emission spectral data derived from the density functional theory,the usefulness of these Ir(Ⅲ)complexes,including(piq)_(2)Ir(acac),(piq)_(2)Ir(tmd),(piq)_(2)Ir(tpip),(fpiq)_(2)Ir(acac),(fpiq)_(2)Ir(tmd),and(fpiq)_(2)Ir(tpip),in OLEDs was examined,where piq=1-phenylisoquinoline,fpiq=1-(4-fluorophenyl)isoquinoline,acac=(3Z)-4-hydroxypent-3-en-2-one,tmd=(4Z)-5-hydroxy-2,2,6,6-tetramethylhept-4-en-3-one,and tpip=tetraphenylimido-diphosphonate.These complexes all have low-efficiency roll-off properties,especially(fpiq)_(2)Ir(tpip).Some researchers have successfully synthesized complexes extremely similar to(piq)_(2)Ir(acac)through the Suzuki-Miyaura coupling reaction.展开更多
To mitigate the harmful effects of Al_(2)O_(3) inclusions in steel,it is necessary to conduct comprehensive research on the mechanisms and kinetic laws of Al_(2)O_(3) inclusion modification by Ce.Combined with laborat...To mitigate the harmful effects of Al_(2)O_(3) inclusions in steel,it is necessary to conduct comprehensive research on the mechanisms and kinetic laws of Al_(2)O_(3) inclusion modification by Ce.Combined with laboratory experiments,first-principles calculations,and molecular dynamics simulations,the kinetic model of Ce modification for Al_(2)O_(3) inclusions was established.Based on first-principles calculations,differential charge analysis,density of states analysis,and adsorption energy analysis were performed on the transformation process from Al_(2)O_(3) to CeAlO_(3) at the atomic scale,and the microscopic transformation mechanism of inclusions at the atomic scale was obtained.Molecular dynamics simulations and the solution of mean square displacement function show that the diffusion coefficient for Ce atoms was 2.169×10^(−4) cm^(2)/s,which agreed well with experimental results.In this model,the rate-determining step is the diffusion of Ce atoms across Ce–Al–O inclusions.The relationship between the conversion rate,refining time,and initial radius was discussed.A refining time of 60 s can completely transform Al_(2)O_(3) inclusions less than 2.56μm into CeAlO_(3) inclusions,while refining time of 1200 s is sufficient to modify inclusions size below 11.47μm.展开更多
Formation and evolution of inclusions in low-aluminum Ti-containing 51CrV4 spring steel under BOF(basic oxygen furnace)–LF(ladle furnace)–CC(continuous casting)process were investigated by industrial trials and ther...Formation and evolution of inclusions in low-aluminum Ti-containing 51CrV4 spring steel under BOF(basic oxygen furnace)–LF(ladle furnace)–CC(continuous casting)process were investigated by industrial trials and thermodynamic calculations.During LF refining,deoxidation products including Al_(2)O_(3),Al_(2)O_(3)–Ti_(3)O_(5)–SiO_(2)–MnO and Al_(2)O_(3)–SiO_(2)–MnO are modified as MgO–Al_(2)O_(3),CaO–Al_(2)O_(3)–SiO_(2),CaO–Al_(2)O_(3)–MgO and CaO–Al_(2)O_(3)–SiO_(2)–MgO.When reoxidation during ladle casting is quite serious,inclusions such as Al_(2)O_(3),Al_(2)O_(3)–Ti_(3)O_(5)–SiO_(2)–MnO,and Al_(2)O_(3)–SiO_(2)–MnO may regenerate.A handful of Ti carried by alloy into liquid steel has less influence on inclusions during LF refining;Ti-containing inclusions mainly transiently exist as an intermediate product of deoxidation process and then are gradually modified by[Al],[Ca]or[Mg].Thermodynamic calculation and experimental results reveal that tundish flux is the main source of reoxidation in ladle casting process.Further calculations taking into account of the influence of inclusions before casting indicate that reoxidation within a certain of degree leads to the generation of a large amount of high melting point inclusions including CaO·2MgO·8Al_(2)O_(3),CaO·MgO·7Al_(2)O_(3),MgO·Al_(2)O_(3),CaO·6Al_(2)O_(3)and Al_(2)O_(3)in molten steel,which is basically consistent with experimental results,and more high melting point inclusions will generate as reoxidation becomes severer.On this basis,severer reoxidation will deplete[Si],[Mn],and[Ti]in steel melt,resulting in the formation of liquid inclusions composed of Al_(2)O_(3)–Ti_(3)O_(5)–SiO_(2)–MnO(–CaO).These results are of guiding significance for controlling inclusions in Al-killed Ti-containing spring steel.展开更多
The extreme removal of SiO2 and MnO inclusions in 304 stainless steel in supergravity fields was investigated using an inhouse high-temperature supergravity equipment.The influences of the gravity coefficient and sepa...The extreme removal of SiO2 and MnO inclusions in 304 stainless steel in supergravity fields was investigated using an inhouse high-temperature supergravity equipment.The influences of the gravity coefficient and separation time on the removal efficiency of the inclusions were studied.After supergravity treatment,the inclusions migrated to the top of the sample and formed large aggregates.Meanwhile,the lower part of the sample was purified considerably and appeared significantly cleaner than the raw material.At the gravity coefficient of 500 and separation time of 600 s,the total oxygen content at the bottom of the sample(position E)decreased from 240 to 28 ppm.This corresponded to a total oxygen removal rate of 88.33%.The volume fraction and number density of inclusions exhibited a gradient distribution along the supergravity direction,with values of 8.5%and 106 mm^(-2) at the top of the sample(position A)and 0.06%and 22 mm^(-2) at its bottom.展开更多
Three efficient methods for the synthesis of a series of Cu(Ⅱ) and Cu(Ⅰ) complexes based on imidazo[1,5-a]pyridine derivatives were developed.These methods include the following:(ⅰ)Cu(Ⅱ) salts were used as metal s...Three efficient methods for the synthesis of a series of Cu(Ⅱ) and Cu(Ⅰ) complexes based on imidazo[1,5-a]pyridine derivatives were developed.These methods include the following:(ⅰ)Cu(Ⅱ) salts were used as metal sources and N,N-dimethylformamide was employed as a solvent as well as a reductant to produce Cu(Ⅰ) complexes.(ⅱ) An iodide-containing compound was utilized as a ligand and iodide source to prepare complexes.An in situ metalligand reaction occurred and an iodide-bridged copper complex was generated.(ⅲ) A series of aldehydes were added to the reaction systems to induce in situ metal-ligand reactions between the aldehydes and the imidazo[1,5-a]pyridine derivatives,producing polydentate ligand scaffolds.Eight complexes were prepared and characterized.The catalytic activities of these complexes toward the ketalization of ketones by ethylene glycol were investigated.With the exception of complex4,the remaining seven complexes all showed high catalytic activity.The lower activity of 4 may be due to the larger radius of bridging iodide ions and the shorter Cu(Ⅰ)…Cu(Ⅰ) distance.CCDC:2357696,1·2CH_(2)Cl_(2);2357697,2;2018292,3;2092192,4;2092190,5;2155557,6;2406155,7;2406156,8·EtOH.展开更多
Sensitization of metal-centered forbidden transitions is of great significance.Solid MnII-based phosphors with d-d forbidden transition sensitized by CeIIIwith d-f allowed transition are promising light conversion mat...Sensitization of metal-centered forbidden transitions is of great significance.Solid MnII-based phosphors with d-d forbidden transition sensitized by CeIIIwith d-f allowed transition are promising light conversion materials,but the energy transfer mechanism in CeIII-MnIIis still in dispute for the uncertainty of distances between metal centers.Herein,for the first time,we explored the energy transfer mechanism in two well-designed luminescent heteronuclear complexes with clear crystal structures,i.e.,Ce-N8-Mn and Ce-N2O6-Mn(N8=1,4,7,10,13,16,21,24-octaazabicyclo[8.8.8]hexacosane;N2O6=4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane).Short distances between metal centers facilitate efficient energy transfer from CeIIIto MnIIin both complexes,resulting in high photoluminescence quantum yield up to unity.After systematic study of the two heteronuclear complexes as well as two reference complexes Ce(N8)Br3and Ce(N2O6)Br3,we concluded that dipole-quadrupole interaction is the dominant energy transfer mechanism in the heteronuclear complexes.展开更多
Organoboron compounds have become important intermediates for the construction of new compounds in synthetic chemistry and pharmaceutical chemistry,and it has been found that pinacol biborate(B_(2)pin_(2))as the boron...Organoboron compounds have become important intermediates for the construction of new compounds in synthetic chemistry and pharmaceutical chemistry,and it has been found that pinacol biborate(B_(2)pin_(2))as the boron source and Cu^(Ⅱ) organophosphorus complex(L)as the catalyst can effectively realize the hydrogen-reduced borylation products and dehydrohydrated borylation products of aryl olefins.The reaction regioselectivity involvingβ-C positions of aryl olefins can be controlled by regulating the ligand and additive types.The formation mechanism of the product is conducted at LCu^(Ⅰ)Bpin formed from Cu^(Ⅱ),L and B_(2)pin_(2).Subsequently the substrate aryl olefins undergo addition reaction to form the active intermediate PhCH(LCu^(Ⅰ))CH_(2)Bpin.Followed by the metathesis of the active intermediate with water to form hydrogen reduction products,the same active intermediate can be oxidized with 2,2,6,6-tetramethylpiperidoxyl(TEMPO)to form trans dehydrogenation products.展开更多
基金Academic Fund for Students of Foshan University in 2024(Project No.:xsjj202409zrb11)。
文摘Trimethoprim(TMP),as a broad-spectrum bacteriostatic antibiotic,is widely used in clinical anti-infection therapy and livestock breeding.However,its low water solubility leads to insufficient bioavailability,which has become a key problem restricting its development.Cyclodextrins and their derivatives,with their unique cyclic structures,can form inclusion complexes with TMP to improve its properties.This article reviews the pharmacological characteristics of TMP,the types and properties of common cyclodextrins,focusing on introducing various preparation methods of trimethoprim cyclodextrin inclusion complexes and multiple characterization methods for identifying the inclusion complexes,aiming to provide a reference for further research and development of trimethoprim cyclodextrin inclusion complexes.
文摘To expand the study on the structures and biological activities of the anthracyclines anticancer drugs and reduce their toxic side effects,the new anthraquinone derivatives,9‑pyridylanthrahydrazone(9‑PAH)and 9,10‑bispyridylanthrahydrazone(9,10‑PAH)were designed and synthesized.Utilizing 9‑PAH and 9,10‑PAH as promising anticancer ligands,their respective copper complexes,namely[Cu(L1)Cl_(2)]Cl(1)and{[Cu_(4)(μ_(2)‑Cl)_(3)Cl_(4)(9,10‑PAH)_(2)(DMSO)_(2)]Cl_(2)}_(n)(2),were subsequently synthesized,where the new ligand L1 is formed by coupling two 9‑PAH ligands in the coordination reaction.The chemical and crystal structures of 1 and 2 were elucidated by IR,MS,elemental analysis,and single‑crystal X‑ray diffraction.Complex 1 forms a mononuclear structure.L1 coordinates with Cu through its three N atoms,together with two Cl atoms,to form a five‑coordinated square pyramidal geometry.Complex 2 constitutes a polymeric structure,wherein each structural unit centrosymmetrically encompasses two five‑coordinated binuclear copper complexes(Cu1,Cu2)of 9,10‑PAH,with similar square pyramidal geometry.A chlorine atom(Cl_(2)),located at the symmetry center,bridges Cu1 and Cu1A to connect the two binuclear copper structures.Meanwhile,the two five‑coordinated Cu2 atoms symmetrically bridge the adjacent structural units via one coordinated Cl atom,respectively,thus forming a 1D chain‑like polymeric structure.In vitro anticancer activity assessments revealed that 1 and 2 showed significant cytotoxicity even higher than cisplatin.Specifically,the IC_(50)values of 2 against HeLa‑229 and SK‑OV‑3 cancer cell lines were determined to be(5.92±0.32)μmol·L^(-1)and(6.48±0.39)μmol·L^(-1),respectively.2 could also block the proliferation of HeLa‑229 cells in S phase and significantly induce cell apoptosis.In addition,fluorescence quenching competition experiments suggested that 2 might interact with DNA by an intercalative binding mode,offering insights into its underlying anticancer mechanism.CCDC:2388918,1;2388919,2.
基金supported by the National Natural Science Foundation of China(Grant No.:82104399)the Science and Technology Project of Haihe Laboratory of Modern Chinese Medicine,China(Grant No.:22HHZYSS00001).
文摘Parkinson's disease(PD)is a debilitating and progressive neurodegenerative disorder with complex pathology and multiple membrane barriers that hinder drug delivery,resulting in the absence of ideal therapeutic drugs with minimal side effects[1].Recently,natural medicine has garnered significant attention due to its remarkable efficacy and limited side effects.Icariin,a naturally occurring flavonoid,exhibits excellent potential as a therapeutic agent for neurodegenerative disease[2].However,its clinical application is limited by poor water solubility,low bioavailability,and high clearance rates.Here,an aqueous formulation of icariin/hydroxypropyl-β-cyclodextrin(HP-β-CD)supramolecular inclusion complex was obtained to optimize icariin properties.Furthermore,icariin cyclodextrin supramolecular inclusion complex based thermosensitive(icariin gels)was innovated.At lower temperatures,it remained in a liquid phase with high fluidity.Upon reaching the gelation temperature,it underwent a transition to a gel phase with significantly reduced fluidity,which may be suitable for the design of an intranasal delivery system for PD treatment.The innovative approach capitalizes on the exceptional characteristics of HP-β-CD,which was utilized to synergize with nasal delivery for targeted brain delivery and with icariin for PD treatment[3,4].
基金support from the National Key R&D Program(No.2023YFB3709900)the National Natural Science Foundation of China(Grant No.U22A20171)+1 种基金the High Steel Center at the North China University of Technologythe University of Science and Technology Beijing,China.
文摘The dissolution behavior of complex inclusions in refining slag was studied using confocal laser scanning microscope.Based on the dissolution curve of complex inclusions,the main rate-limiting link of CaO-SiO_(2)-Al_(2)O_(3)complex inclusions was the diffusion in the molten slag.The dissolution rate of CaO-SiO_(2)-Al_(2)O_(3)complex inclusions was affected by the composition and size of inclusion.The functional relationship between the dimensionless inclusion capacity(Zh)and the dimensionless dissolution rate(Ry)of CaO-SiO_(2)-Al_(2)O_(3)complex inclusions was calculated as Ry=2.10×10^(-6)Zh^(0.160),while it was Ry=2.10×10^(-6)Zh^(0.0087)for Al_(2)O_(3)-CaO complex inclusions.On this basis,the complete dissolution time and rate of the complex inclusions were calculated by using the function relation between the Zh and Ry numbers.
基金supported by the National Key R&D Program(No.2023YFB3709900)the National Nature Science Foundation of China(No.U22A20171)+2 种基金China Baowu Low Carbon Metallurgy Innovation Foundation(No.BWLCF202315)the High Steel Center(HSC)at North China University of TechnologyUniversity of Science and Technology Beijing,China.
文摘The characteristics of nonmetallic inclusions formed during steel production have a significant influence on steel performance.In this paper,studies on inclusions using confocal scanning laser microscopy(CSLM)are reviewed and summarized,particularly the col-lision of various inclusions,dissolution of inclusions in liquid slag,and reactions between inclusions and steel.Solid inclusions exhibited a high collision tendency,whereas pure liquid inclusions exhibited minimal collisions because of the small attraction force induced by their<90°contact angle with molten steel.The collision of complex inclusions in molten steel was not included in the scope of this study and should be evaluated in future studies.Higher CaO/Al_(2)O_(3)and CaO/SiO_(2)ratios in liquid slag promoted the dissolution of Al_(2)O_(3)-based in-clusions.The formation of solid phases in the slag should be prevented to improve dissolution of inclusions.To accurately simulate the dissolution of inclusions in liquid slag,in-situ observation of the dissolution of inclusions at the steel-slag interface is necessary.Using a combination of CSLM and scanning electron microscopy-energy dispersive spectroscopy,the composition and morphological evolution of the inclusions during their modification by the dissolved elements in steel were observed and analyzed.Although the in-situ observa-tion of MnS and TiN precipitations has been widely studied,the in-situ observation of the evolution of oxide inclusions in steel during so-lidification and heating processes has rarely been reported.The effects of temperature,heating and cooling rates,and inclusion character-istics on the formation of acicular ferrites(AFs)have been widely studied.At a cooling rate of 3-5 K/s,the order of AF growth rate in-duced by different inclusions,as reported in literature,is Ti-O<Ti-Ca-Zr-Al-O<Mg-O<Ti-Zr-Al-O<Mn-Ti-Al-O<Ti-Al-O<Zr-Ti-Al-O.Further comprehensive experiments are required to investigate the quantitative relationship between the formation of AFs and inclusions.
基金the National Natural Science Foundation of China(52004180,52204350)the China Postdoctoral Science Foundation(2020M683706XB)the Research Project Supported by Shanxi Scholarship Council of China(2023-080).
文摘Rare earth La was introduced into 40Cr steel in industrial experiments to achieve the purpose of modifying inclusions.The impact of La on the inclusion modification was studied,and its influence on the solidification structure was further investigated.With adding 0.0023%La,the Al_(2)O_(3)·CaO·CaS inclusions were modified to the LaAlO_(3)·CaO·CaS inclusions.Additionally,the morphology tended to be more spherical,and the proportion of small-sized inclusions increased significantly from 77.8%to 93.5%.The large-sized inclusions were almost completely eliminated.Based on experimental results,a dynamical model elucidating the process of inclusion modification by La was developed.Furthermore,the ratio of equiaxed zone of the solidification structure increased from 22.9%to 31.0%,and the average primary dendrite arm spacing decreased significantly from 288.4 to 226.2μm.Two-dimensional lattice mismatch analysis results determined that LaAlO_(3)can serve as an effective heterogeneous nucleation core,leading to solidification structure refinement.The beneficial transformation of inclusions and refinement of solidification structure are conducive to the cold heading process of 40Cr steel.
基金the support from the National Natural Science Foundation of China(Grant Nos.52074198,52374342,and U21A20113)the Department of Science and Technology of Hubei Province(Grant Nos.2023AFB603 and 2023DJC140).
文摘The transformation mechanism of the inclusions and microstructure in 316L stainless steel after post-isothermal heat treatment(IHT)was revealed,along with the pitting behavior of the inclusions in a chloride environment before and after the transformation.The effect of the inclusion transformation on the pitting corrosion behavior of 316L stainless steel and its intrinsic mechanism was also revealed.Results revealed a gradual transformation of MnO-SiO_(2)inclusions into MnO-Cr_(2)O_(3) within the temperature range of 1373 to 1573 K.MnO-Cr_(2)O_(3)inclusions exhibited minimal dissolution in chloride ion corrosion environments,while MnO-SiO_(2)oxides demonstrated higher electrochemical activity and were more prone to dissolve and form pits.Meanwhile,IHT significantly reduced the dislocation density of stainless steel,rendering it more stable in corrosive environments.X-ray photoelectron spectroscopy peak distributions of the passive films demonstrated that IHT increased the proportion of Cr and Fe oxides and hydroxides in the passive film which improved the stability and corrosion resistance of the steel.
基金support from the National Natural Science Foundation of China(Nos.22277056,21977052)the Distinguished Young Scholars of Jiangsu Province(No.BK20230006)+2 种基金the Natural Science Foundation of Jiangsu Province(Nos.BK20230977,BK20231090)the Natural Science Foundation of the Higher Education Institutions of Jiangsu Province(No.23KJB150020)the Jiangsu Excellent Postdoctoral Program(No.2022ZB758)。
文摘Metal complexes hold significant promise in tumor diagnosis and treatment.However,their potential applications in photodynamic therapy(PDT)are hindered by issues such as poor photostability,low yield of reactive oxygen species(ROS),and aggregation-induced ROS quenching.To address these challenges,we present a molecular self-assembly strategy utilizing aggregation-induced emission(AIE)conjugates for metal complexes.As a proof of concept,we synthesized a mitochondrial-targeting cyclometalated Ir(Ⅲ)photosensitizer Ir-TPE.This approach significantly enhances the photodynamic effect while mitigating the dark toxicity associated with AIE groups.Ir-TPE readily self-assembles into nanoaggregates in aqueous solution,leading to a significant production of ROS upon light irradiation.Photoirradiated Ir-TPE triggers multiple modes of death by excessively accumulating ROS in the mitochondria,resulting in mitochondrial DNA damage.This damage can lead to ferroptosis and autophagy,two forms of cell death that are highly cytotoxic to cancer cells.The aggregation-enhanced photodynamic effect of Ir-TPE significantly enhances the production of ROS,leading to a more pronounced cytotoxic effect.In vitro and in vivo experiments demonstrate this aggregation-enhanced PDT approach achieves effective in situ tumor eradication.This study not only addresses the limitations of metal complexes in terms of low ROS production due to aggregation but also highlights the potential of this strategy for enhancing ROS production in PDT.
基金Supported by NSFC(No.12171062)the Natural Science Foundation of Chongqing(No.CSTB2022NSCQ-JQX0004)+1 种基金the Chongqing Talent Support Program(No.cstc2024ycjh-bgzxm0121)Science and Technology Project of Chongqing Education Committee(No.KJZD-M202300503)。
文摘The purpose of this article is to introduce a new method with a self-adaptive stepsize for approximating a common solution of monotone inclusion problems and variational inequality problems in reflexive Banach spaces.The strong convergence result for our method is established under some standard assumptions without any requirement of the knowledge of the Lipschitz constant of the mapping.Several numerical experiments are provided to verify the advantages and efficiency of proposed algorithms.
文摘Two novel lanthanide complexes,[Sm_(2)(BA)_(6)(4-OH-terpy)_(2)]·2H_(2)O·2EtOH(1)and[Pr_(2)(BA)_(6)(4-OH-terpy)_(2)(H_(2)O)_(2)]·HBA·H_(2)O(2),where HBA=benzoic acid,4-OH-terpy=4-hydroxy-2,2'∶6',2″-terpyridine,were successfully synthesized using ultrasonic dissolution and the conventional solution method with two mixed ligands HBA and 4-OH-terpy.During the synthesis,4-OH-terpy was involved in the reaction as a neutral ligand,while HBA,in its deprotonated form(BA-),coordinated with the lanthanide ions as an acidic ligand.The crystal structures of these two complexes were precisely determined by single-crystal X-ray diffraction.Elemental analysis,infrared and Raman spectroscopy,and powder X-ray diffraction techniques were also employed to further explore the physicochemical properties of the two complexes.The single-crystal X-ray diffraction data indicate that,despite their structural differences,both complexes belong to the triclinic crystal system P1 space group.The central lanthanide ions have the same coordination number but exhibit different coordination environments.To comprehensively evaluate the thermal stability of these two complexes,comprehensive tests including thermogravimetric analysis,differential thermogravimetric analysis,differential scanning calorimetry,Fourier transform infrared spectroscopy,and mass spectrometry were conducted.Meanwhile,an in-depth investigation was conducted into the 3D infrared stacked images and mass spectra of the gases emitted from the complexes.In addition,studies of the fluorescence properties of complex1 showed that it exhibited fluorescence emission matching the Sm^(3+)characteristic transition.
文摘To extend a new family of aminophosphine-coordinated[FeFe]-hydrogenase mimics for catalytic hydro-gen(H_(2))evolution,we carried out the ligand substitutions of diiron hexacarbonyl precursors[Fe_(2)(μ-X_(2)pdt)(CO)_(6)](X_(2)pdt=(SCH_(2))_(2)CX_(2),X=Me,H)with aminodiphosphines(Ph_(2)PCH_(2))_(2)NY(Y=(CH_(2))_(2)OH,(CH_(2))_(3)OH)to obtain two new diiron aminophosphine complexes[Fe_(2)(L1)(μ-Me_(2)pdt)(CO)_(5)](1)and[Fe_(2)(L2)(μ-H_(2)pdt)(CO)_(5)](2),where L1=3-[(diphe-nylphosphaneyl)methyl]oxazolidine,L2=3-[(diphenylphosphaneyl)methyl]-1,3-oxazinane.Moreover,the structures of 1 and 2 have been fully confirmed by elemental analysis,spectroscopic techniques,and single-crystal X-ray diffraction.Using cyclic voltammetry(CV),we investigated the electrochemical redox performance and proton reduc-tion activities of 1 and 2 in acetic acid(HOAc).The CV study indicates that diiron aminophosphine complexes 1 and 2 can be considered to be hydrogenase-inspired diiron molecular electrocatalysts for the reduction of protons into H 2 generation in the presence of HOAc.CCDC:2443967,1;2443969,2.
基金Project supported by the National Natural Science Foundation of China(52174323,52231003)。
文摘In order to mitigate the harm of alumina,calcium aluminate,and magnesium aluminum spinel inclusions on the fatigue performance of bearing steel,the effect of Ce-Mg composite treatment on the cleanliness of silicon-killed GCr15 bearing steel and the evolution of Ce-Mg-Mn-O-S composite inclusions during heat treatment of the steels at 1523 K were investigated in this present work.The results indicate that the cleanliness of S2 with 0.0045 wt%Ce and 0.0016 wt%Mg is better than that in S1 with0.0020 wt%Ce and 0.0011 wt%Mg,which is attributed to the more effective removal of Ce-Mg-Mn-O-S composite inclusions,with help of good aggregation capacity of Ce-containing inclusions and small volume density of Mg-containing inclusions,due to the increase of rare earth and magnesium content.The aspect ratio and area fraction of the Ce-Mg-Mn-O-S composite inclusions in as-cast steel decrease significantly with isothermal treatment at 1523 K for 150 min,due to the effect of(ⅰ)Ostwald aging mechanism of inclusions and(ⅱ)sulfide solid solution during isothermal treatment.With the increase of isothermal treatment time from 150 to 550 min,the aspect ratio and area fraction of the inclusions in SO(untreated steel)and S1 decrease slightly,because spheroidization and solid solution of inclusions reach their basic equilibrium at 1523 K.However,the aspect ratio and area fraction of the Ce-Mg-Mn-O-S composite inclusions in S2 actually increase,and the inclusions evolve into three-phase(two-phase)inclusions,which is attributed to(ⅲ)transformation of phase compositions in inclusions and interfacial reaction between inclusions and steel matrix during isothermal heating.Therefore,the control of inclusions in silicon-killed bearing steel with Ce and Mg composite treatment should be combined with specific heat treatment processes and appropriate rare earth and magnesium contents,to minimize the damage of inclusions on the fatigue performance of bearing steel products.
文摘Two Gd_(2)complexes,namely[Gd_(2)(dbm)_(2)(HL_(1))_(2)(CH_(3)OH)_(2)]·4CH_(3)OH(1)and[Gd_(2)(dbm)_(2)(L_(2))_(2)(CH_(3)OH)_(2)]·2CH_(3)OH(2),where H_(3)L_(1)=(Z)-N'-[4-(diethylamino)-2-hydroxybenzylidene]-2-hydroxyacetohydrazide,H_(2)L_(2)=(E)-N'-(5-bromo-2-hydroxy-3-methoxybenzylidene)nicotinohydrazide,Hdbm=dibenzoylmethane,have been constructed by adopting the solvothermal method.Structural characterization unveils that both complexes 1 and 2 are constituted by two Gd^(3+)ions,two dbm-ions,two CH_(3)OH molecules,and two polydentate Schiff-base ligands(HL_(1)^(2-)or L_(2)^(2-)).In addition,complex 1 contains four free methanol molecules,whereas complex 2 harbors two free methanol molecules.By investigating the interactions between complexes 1 and 2 and four types of bacteria(Bacillus subtilis,Escherichia coli,Staphylococcus aureus,Candida albicans),it was found that both complexes 1 and 2 exhibited potent antibacte-rial activities.The interaction mechanisms between the ligands H_(3)L_(1),H_(2)L_(2),complexes 1 and 2,and calf thymus DNA(CT-DNA)were studied using ultraviolet-visible spectroscopy,fluorescence titration,and cyclic voltammetry.The results demonstrated that both complexes 1 and 2 can intercalate into CT-DNA molecules,thereby inhibiting bacterial proliferation to achieve the antibacterial effects.CCDC:2401116,1;2401117,2.
文摘We have examined the theoretical implications of combining two main and three auxiliary ligands to form several Ir(Ⅲ)complexes featuring a transition metal as their core atom to identify some appropriate organic lightemitting diode(OLED)materials.By utilizing electronic structure,frontier molecular orbitals,minimum single-line absorption,triplet excited states,and emission spectral data derived from the density functional theory,the usefulness of these Ir(Ⅲ)complexes,including(piq)_(2)Ir(acac),(piq)_(2)Ir(tmd),(piq)_(2)Ir(tpip),(fpiq)_(2)Ir(acac),(fpiq)_(2)Ir(tmd),and(fpiq)_(2)Ir(tpip),in OLEDs was examined,where piq=1-phenylisoquinoline,fpiq=1-(4-fluorophenyl)isoquinoline,acac=(3Z)-4-hydroxypent-3-en-2-one,tmd=(4Z)-5-hydroxy-2,2,6,6-tetramethylhept-4-en-3-one,and tpip=tetraphenylimido-diphosphonate.These complexes all have low-efficiency roll-off properties,especially(fpiq)_(2)Ir(tpip).Some researchers have successfully synthesized complexes extremely similar to(piq)_(2)Ir(acac)through the Suzuki-Miyaura coupling reaction.
基金supported by the National Natural Science Foundation of China(Nos.52064011,52274331 and 52264041)Guizhou Provincial Basic Research Program(Natural Science)(Nos.ZK[2021]258 and ZK[2023]Zhongdian 020)+6 种基金Guizhou Provincial Key Technology R&D Program(No.[2021]342)Guizhou Provincial Program on Commercialization of Scientific and Technological Achievements(No.[2022]089)supported by Open Project of State Key Laboratory of Advanced Special Steel,Shanghai Key Laboratory of Advanced Ferrometallurgy,Shanghai University(No.SKLASS 2023-08)the Science and Technology Commission of Shanghai Municipality(No.19DZ2270200)supported by State Key Laboratory of Advanced Metallurgy(No.K23-04)China Postdoctoral Science Foundation(No.2023MD744232)Key Research Projects in Higher Education Institutions of Henan Province(No.24B450003).
文摘To mitigate the harmful effects of Al_(2)O_(3) inclusions in steel,it is necessary to conduct comprehensive research on the mechanisms and kinetic laws of Al_(2)O_(3) inclusion modification by Ce.Combined with laboratory experiments,first-principles calculations,and molecular dynamics simulations,the kinetic model of Ce modification for Al_(2)O_(3) inclusions was established.Based on first-principles calculations,differential charge analysis,density of states analysis,and adsorption energy analysis were performed on the transformation process from Al_(2)O_(3) to CeAlO_(3) at the atomic scale,and the microscopic transformation mechanism of inclusions at the atomic scale was obtained.Molecular dynamics simulations and the solution of mean square displacement function show that the diffusion coefficient for Ce atoms was 2.169×10^(−4) cm^(2)/s,which agreed well with experimental results.In this model,the rate-determining step is the diffusion of Ce atoms across Ce–Al–O inclusions.The relationship between the conversion rate,refining time,and initial radius was discussed.A refining time of 60 s can completely transform Al_(2)O_(3) inclusions less than 2.56μm into CeAlO_(3) inclusions,while refining time of 1200 s is sufficient to modify inclusions size below 11.47μm.
基金support from the project of Xinjiang Bayi Iron and Steel Co.,Ltd.(No.2022-0460).
文摘Formation and evolution of inclusions in low-aluminum Ti-containing 51CrV4 spring steel under BOF(basic oxygen furnace)–LF(ladle furnace)–CC(continuous casting)process were investigated by industrial trials and thermodynamic calculations.During LF refining,deoxidation products including Al_(2)O_(3),Al_(2)O_(3)–Ti_(3)O_(5)–SiO_(2)–MnO and Al_(2)O_(3)–SiO_(2)–MnO are modified as MgO–Al_(2)O_(3),CaO–Al_(2)O_(3)–SiO_(2),CaO–Al_(2)O_(3)–MgO and CaO–Al_(2)O_(3)–SiO_(2)–MgO.When reoxidation during ladle casting is quite serious,inclusions such as Al_(2)O_(3),Al_(2)O_(3)–Ti_(3)O_(5)–SiO_(2)–MnO,and Al_(2)O_(3)–SiO_(2)–MnO may regenerate.A handful of Ti carried by alloy into liquid steel has less influence on inclusions during LF refining;Ti-containing inclusions mainly transiently exist as an intermediate product of deoxidation process and then are gradually modified by[Al],[Ca]or[Mg].Thermodynamic calculation and experimental results reveal that tundish flux is the main source of reoxidation in ladle casting process.Further calculations taking into account of the influence of inclusions before casting indicate that reoxidation within a certain of degree leads to the generation of a large amount of high melting point inclusions including CaO·2MgO·8Al_(2)O_(3),CaO·MgO·7Al_(2)O_(3),MgO·Al_(2)O_(3),CaO·6Al_(2)O_(3)and Al_(2)O_(3)in molten steel,which is basically consistent with experimental results,and more high melting point inclusions will generate as reoxidation becomes severer.On this basis,severer reoxidation will deplete[Si],[Mn],and[Ti]in steel melt,resulting in the formation of liquid inclusions composed of Al_(2)O_(3)–Ti_(3)O_(5)–SiO_(2)–MnO(–CaO).These results are of guiding significance for controlling inclusions in Al-killed Ti-containing spring steel.
基金supported by the National Natural Science Foundation of China(No.52174275).
文摘The extreme removal of SiO2 and MnO inclusions in 304 stainless steel in supergravity fields was investigated using an inhouse high-temperature supergravity equipment.The influences of the gravity coefficient and separation time on the removal efficiency of the inclusions were studied.After supergravity treatment,the inclusions migrated to the top of the sample and formed large aggregates.Meanwhile,the lower part of the sample was purified considerably and appeared significantly cleaner than the raw material.At the gravity coefficient of 500 and separation time of 600 s,the total oxygen content at the bottom of the sample(position E)decreased from 240 to 28 ppm.This corresponded to a total oxygen removal rate of 88.33%.The volume fraction and number density of inclusions exhibited a gradient distribution along the supergravity direction,with values of 8.5%and 106 mm^(-2) at the top of the sample(position A)and 0.06%and 22 mm^(-2) at its bottom.
文摘Three efficient methods for the synthesis of a series of Cu(Ⅱ) and Cu(Ⅰ) complexes based on imidazo[1,5-a]pyridine derivatives were developed.These methods include the following:(ⅰ)Cu(Ⅱ) salts were used as metal sources and N,N-dimethylformamide was employed as a solvent as well as a reductant to produce Cu(Ⅰ) complexes.(ⅱ) An iodide-containing compound was utilized as a ligand and iodide source to prepare complexes.An in situ metalligand reaction occurred and an iodide-bridged copper complex was generated.(ⅲ) A series of aldehydes were added to the reaction systems to induce in situ metal-ligand reactions between the aldehydes and the imidazo[1,5-a]pyridine derivatives,producing polydentate ligand scaffolds.Eight complexes were prepared and characterized.The catalytic activities of these complexes toward the ketalization of ketones by ethylene glycol were investigated.With the exception of complex4,the remaining seven complexes all showed high catalytic activity.The lower activity of 4 may be due to the larger radius of bridging iodide ions and the shorter Cu(Ⅰ)…Cu(Ⅰ) distance.CCDC:2357696,1·2CH_(2)Cl_(2);2357697,2;2018292,3;2092192,4;2092190,5;2155557,6;2406155,7;2406156,8·EtOH.
基金financial support from the National Key R&D Program of China(Nos.2022YFB3503702,2023YFB3506901,2021YFB3501800)the National Natural Science Foundation of China(Nos.92156016,62104013,22071003)。
文摘Sensitization of metal-centered forbidden transitions is of great significance.Solid MnII-based phosphors with d-d forbidden transition sensitized by CeIIIwith d-f allowed transition are promising light conversion materials,but the energy transfer mechanism in CeIII-MnIIis still in dispute for the uncertainty of distances between metal centers.Herein,for the first time,we explored the energy transfer mechanism in two well-designed luminescent heteronuclear complexes with clear crystal structures,i.e.,Ce-N8-Mn and Ce-N2O6-Mn(N8=1,4,7,10,13,16,21,24-octaazabicyclo[8.8.8]hexacosane;N2O6=4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane).Short distances between metal centers facilitate efficient energy transfer from CeIIIto MnIIin both complexes,resulting in high photoluminescence quantum yield up to unity.After systematic study of the two heteronuclear complexes as well as two reference complexes Ce(N8)Br3and Ce(N2O6)Br3,we concluded that dipole-quadrupole interaction is the dominant energy transfer mechanism in the heteronuclear complexes.
文摘Organoboron compounds have become important intermediates for the construction of new compounds in synthetic chemistry and pharmaceutical chemistry,and it has been found that pinacol biborate(B_(2)pin_(2))as the boron source and Cu^(Ⅱ) organophosphorus complex(L)as the catalyst can effectively realize the hydrogen-reduced borylation products and dehydrohydrated borylation products of aryl olefins.The reaction regioselectivity involvingβ-C positions of aryl olefins can be controlled by regulating the ligand and additive types.The formation mechanism of the product is conducted at LCu^(Ⅰ)Bpin formed from Cu^(Ⅱ),L and B_(2)pin_(2).Subsequently the substrate aryl olefins undergo addition reaction to form the active intermediate PhCH(LCu^(Ⅰ))CH_(2)Bpin.Followed by the metathesis of the active intermediate with water to form hydrogen reduction products,the same active intermediate can be oxidized with 2,2,6,6-tetramethylpiperidoxyl(TEMPO)to form trans dehydrogenation products.
