The mononuclear copper（Ⅱ） complex [Cu（L）（2-AP）] 1 and binuclear copper（Ⅱ） complex [Cu（L）（py）]2 2 （L = C10H11O5NS, taurine o-vanillin, py = prydine, 2-AP = 2-aminopyridine） with mixed ligand have been s...The mononuclear copper（Ⅱ） complex [Cu（L）（2-AP）] 1 and binuclear copper（Ⅱ） complex [Cu（L）（py）]2 2 （L = C10H11O5NS, taurine o-vanillin, py = prydine, 2-AP = 2-aminopyridine） with mixed ligand have been synthesized and characterized by X-ray diffraction method. Crystal data for 1： orthorhombic, space group Pbca with a = 11.921（4）, b = 15.816（6）, c = 17.076（6） A, V= 3219.7（19） A^3, C15H17CuN3O5S, Z = 8, Mr = 414.92, De = 1.712 g/cm^3,μ（MoKα） = 1.520 mm^-1, F（000） = 1704, the final R = 0.0300 and wR = 0.0705 for 2840 observed reflections with I 〉 2σ（I）; and crystal data for 2： monoclinic, space group P21/c with a = 7.929（3）, b = 17.038（5）, c = 11.734（4） A, β = 98.162（6）°, V = 1569.1（9） A^3, C15H16CuN2O5S, Z = 4, Mr = 399.90, Dc = 1.693 g/cm^3, F（000） = 820,μ（MoKα） = 1.554 mm^-1, the final R = 0.0351 and wR = 0.0848 for 2767 observed reflections （I 〉 2σ（I））. The molecular structure of complex 1 consists of one tetra-coordinated Cu（Ⅱ） atom generating a slightly distorted square plane, and a one-dimensional chain structure is formed by intermolecular hydrogen bonds. Complex 2 consists of a diphenolic hydroxyl O-bridged binuclear copper（Ⅱ） structure. The crystal structures of complexes 1 and 2 reveal that the coordinate copper centers are bound to both nitrogen and oxygen atom donors. The usual N,O-trans arrangement of ligands is observed in both cases.展开更多
Two novel mixed-ligand complexes, [M（phen）2（ans）2]·H2O （M = Cd（Ⅱ） 1, Zn（Ⅱ） 2; phen is 1, 10-phenanthroline, and ans is 4-aminonaphthalene-1-sulfonate）, were obtained from the reaction of 1, 10-phenant...Two novel mixed-ligand complexes, [M（phen）2（ans）2]·H2O （M = Cd（Ⅱ） 1, Zn（Ⅱ） 2; phen is 1, 10-phenanthroline, and ans is 4-aminonaphthalene-1-sulfonate）, were obtained from the reaction of 1, 10-phenanthroline, sodium 4-aminonaphthalene-1-sulfonate tetrahydrate and acetate in mixed solvents. Interaction of the complexes with calf thymus DNA （ctDNA） were investigated using UV-vis absorption spectra, luminescence titrations, steady-state emission quenching by [Fe（CN）6]4 , DNA competitive binding with ethidium bromide （EB） and viscosity measurements. The experimental results indicate that there exist two interaction modes between the complexes and DNA, namely the electrostatic interaction and intercalation, with the binding constants of 1.82 × 10^5 M-1 for 1 and 4.78 ×10^4 M^- 1 for 2 in buffer of 50 mM NaCl and 5 mM Tris-HCI （pH 7.0）.展开更多
Five triboluminescent mixed-ligand complexes of Eu^(3+)with thenoyltrifluoroacetone(TTA)and pyridine-N-oxide or its substitutive derivatives have been prepared.They are all pale yellow crystalline com- pounds with the...Five triboluminescent mixed-ligand complexes of Eu^(3+)with thenoyltrifluoroacetone(TTA)and pyridine-N-oxide or its substitutive derivatives have been prepared.They are all pale yellow crystalline com- pounds with the formula of Eu(TTA)_3·L(L=py NO.2-pie NO,3-pie NO,4-pic NO,bipy N_2O_2).Their physico-chemical properties have been studied with conductometry,UV and IR absorption and fluorescence spectroscopy.Once the complexes are touched or rubbed by a glass rod,they emit strong red triboluminescent light which is similar to the characteristic fluorescence of Eu^(3+).展开更多
Three copper(Ⅱ),nickel and cadmium(Ⅱ)complexes,namely[Cu_(2)(μ-H2dbda)2(phen)2]·2H_(2)O(1),[Ni(μ-H2dbda)(μ-bpb)(H_(2)O)2]n(2),and[Cd(μ-H2dbda)(μ-bpa)]n(3),have been constructed hydrothermally using H4dbda(...Three copper(Ⅱ),nickel and cadmium(Ⅱ)complexes,namely[Cu_(2)(μ-H2dbda)2(phen)2]·2H_(2)O(1),[Ni(μ-H2dbda)(μ-bpb)(H_(2)O)2]n(2),and[Cd(μ-H2dbda)(μ-bpa)]n(3),have been constructed hydrothermally using H4dbda(4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid),phen(1,10-phenanthroline),bpb(1,4-bis(pyrid-4-yl)benzene),bpa(bis(4-pyridyl)amine),and copper,nickel and cadmium chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and singlecrystal X-ray diffraction analyses.Single-crystal X-ray diffraction analyses revealed that three complexes crystallize in the monoclinic P21/n,tetragonal I42d,and orthorhombic P21212 space groups.The complexes exhibit molecular dimers(1)or 2D metal-organic networks(2 and 3).The catalytic performances in the Knoevenagel reaction of these complexes were investigated.Complex 1 exhibits an effective catalytic activity and excellent reusability as a heterogeneous catalyst in the Knoevenagel reaction at room temperature.CCDC:2463800,1;2463801,2;2463802,3.展开更多
Six new lanthanide complexes:[Ln(3,4-DEOBA)3(4,4'-DM-2,2'-bipy)]2·2C_(2)H_(5)OH,[Ln=Dy(1),Eu(2),Tb(3),Sm(4),Ho(5),Gd(6);3,4-DEOBA-=3,4-diethoxybenzoate,4,4'-DM-2,2'-bipy=4,4'-dimethyl-2,2'...Six new lanthanide complexes:[Ln(3,4-DEOBA)3(4,4'-DM-2,2'-bipy)]2·2C_(2)H_(5)OH,[Ln=Dy(1),Eu(2),Tb(3),Sm(4),Ho(5),Gd(6);3,4-DEOBA-=3,4-diethoxybenzoate,4,4'-DM-2,2'-bipy=4,4'-dimethyl-2,2'-bipyridine]were successfully synthesized by the volatilization of the solution at room temperature.The crystal structures of six complexes were determined by single-crystal X-ray diffraction technology.The results showed that the complexes all have a binuclear structure,and the structures contain free ethanol molecules.Moreover,the coordination number of the central metal of each structural unit is eight.Adjacent structural units interact with each other through hydrogen bonds and further expand to form 1D chain-like and 2D planar structures.After conducting a systematic study on the luminescence properties of complexes 1-4,their emission and excitation spectra were obtained.Experimental results indicated that the fluorescence lifetimes of complexes 2 and 3 were 0.807 and 0.845 ms,respectively.The emission spectral data of complexes 1-4 were imported into the CIE chromaticity coordinate system,and their corre sponding luminescent regions cover the yellow light,red light,green light,and orange-red light bands,respectively.Within the temperature range of 299.15-1300 K,the thermal decomposition processes of the six complexes were comprehensively analyzed by using TG-DSC/FTIR/MS technology.The hypothesis of the gradual loss of ligand groups during the decomposition process was verified by detecting the escaped gas,3D infrared spectroscopy,and ion fragment information detected by mass spectrometry.The specific decomposition path is as follows:firstly,free ethanol molecules and neutral ligands are removed,and finally,acidic ligands are released;the final product is the corresponding metal oxide.CCDC:2430420,1;2430422,2;2430419,3;2430424,4;2430421,5;2430423,6.展开更多
Three zinc(Ⅱ),nickel(Ⅱ),and cadmium(Ⅱ)complexes,namely[Zn(μ-Htpta)(py)_(2)]n(1),[Ni(H_(2)biim)2(H_(2)O)2][Ni(tpta)(H_(2)biim)2(H_(2)O)]2·3H_(2)O(2),and[Cd_(3)(μ4-tpta)2(μ-dpe)_(3)]_(n)(3),have been construc...Three zinc(Ⅱ),nickel(Ⅱ),and cadmium(Ⅱ)complexes,namely[Zn(μ-Htpta)(py)_(2)]n(1),[Ni(H_(2)biim)2(H_(2)O)2][Ni(tpta)(H_(2)biim)2(H_(2)O)]2·3H_(2)O(2),and[Cd_(3)(μ4-tpta)2(μ-dpe)_(3)]_(n)(3),have been constructed hydrothermally at 160℃ using H_(3)tpta([1,1':3',1″-terphenyl]-4,4',5'-tricarboxylic acid),py(pyridine),H_(2)biim(2,2'-biimidazole),dpe(1,2-di(4-pyridyl)ethylene),and zinc,nickel and cadmium chlorides,resulting in the formation of stable crystalline solids which were subsequently analyzed using infrared spectroscopy,element analysis,thermogravimetric analysis,as well as structural analyses conducted via single-crystal X-ray diffraction.The findings from these single-crystal Xray diffraction studies indicate that complexes 1-3 form crystals within the monoclinic system P2_(1)/c space group(1)or triclinic system P1 space group(2 and 3),and possess 1D,0D,and 3D structures,respectively.Complex 1 demonstrated substantial catalytic efficiency and excellent reusability as a heterogeneous catalyst in the reaction of Knoevenagel condensation under ambient temperature conditions.In addition,complex 1 also showcased notable anti-wear performance when used in polyalphaolefin synthetic lubricants.CCDC:2449810,1;2449811,2;2449812,3.展开更多
This paper reports the preparation of three di‑iron complexes containing a thiazole moiety.Esterification of complex[Fe_(2)(CO)_(6)(μ‑SCH_(2)CH(CH_(2)OH)S)](1)with 4‑methylthiazole‑5‑carboxylic acid gave the correspo...This paper reports the preparation of three di‑iron complexes containing a thiazole moiety.Esterification of complex[Fe_(2)(CO)_(6)(μ‑SCH_(2)CH(CH_(2)OH)S)](1)with 4‑methylthiazole‑5‑carboxylic acid gave the corresponding ester[Fe_(2)(CO)_(6)(μ‑tedt)](2),where tedt=SCH_(2)CH(CH_(2)OOC(5‑C_(3)HNSCH_(3)))S.Further reactions of complex 2 with tri(ptolyl)phosphine(tp)or tris(4‑fluorophenyl)phosphine(fp)gave the phosphine‑substituted derivatives[Fe_(2)(CO)_(5)(tp)(μ‑tedt)](3)and[Fe_(2)(CO)_(5)(fp)(μ‑tedt)](4).The structures of the newly prepared complexes were elucidated by elemental analysis,NMR,IR,and X‑ray photoelectron spectroscopy.Moreover,single‑crystal X‑ray diffraction analysis confirmed their molecular structures,showing that they contain a di‑iron core ligated by a bridged dithiolate bearing a thiazole moiety and terminal carbonyls.The electrochemical and electrocatalytic proton reduction were probed by cyclic voltammetry,revealing that three complexes can catalyze the reduction of protons to H_(2) under the electrochemical conditions.For comparison,complex 4 possessed the best efficiency with a turnover frequency of 23.5 s^(-1)at 10 mmol·L^(-1)HOAc concentration.In addition,the fungicidal activity of these complexes was also investigated in this study.CCDC:2477511,2;2477512,3;2477513,4.展开更多
While biomaterials are endowed with sophisticated functions by the temporal dynamics and autonomy derived from non-equilibrium assemblies in biological systems,fabricating advanced materials counterparts with these fe...While biomaterials are endowed with sophisticated functions by the temporal dynamics and autonomy derived from non-equilibrium assemblies in biological systems,fabricating advanced materials counterparts with these features through kinetic control remains rare.Herein,we report a non-equilibrium hydrogel that exhibits autonomous time-dependent ultrabright fluorescence(quantum yield 0.90),achieved through the kinetically controlled incorporation of thermodynamic equilibrium host-vip complexes into a poly(2-hydroxyethyl methacrylate)(PHEMA)network.Transient complexes are programmed by coupling rapid assembly kinetics with the slow competitive binding of the polymer matrix.This kinetic mismatch converts a thermodynamic equilibrium supramolecular system into a non-equilibrium state,generating temporally dynamic fluorescence that cyclically shifts from yellow to green and self-reverts.The programmed temporal dynamics endow the hydrogel with high potential for information encryption applications.展开更多
The complexes 1-4 of cyclobutanocucurbit[5]uril(CyB5Q[5])with Na^(+)/K^(+)have been synthesized and characterized by single-crystal X-ray diffraction.The results show that although the inorganic salts are used when th...The complexes 1-4 of cyclobutanocucurbit[5]uril(CyB5Q[5])with Na^(+)/K^(+)have been synthesized and characterized by single-crystal X-ray diffraction.The results show that although the inorganic salts are used when the cations are the same and the anions are different,in complex 1,Na^(+)closes one port of CyB5Q[5]through Na—O seven coordination bonds to form a molecular bowl;in complex 3,Na^(+)completely closes the two ports of CyB5Q[5]to form a molecular capsule with six Na—O coordination bonds;in complexes 2 and 4,the two ports of CyB5Q[5]are completely closed to form K—O coordinated molecular capsules,but the K^(+)of complex 2 is six-coordinated and that of complex 4 is eight-/nine-coordinated.and complex 4 are connected by three oxygen bridges to form a 1D molecular chain.CCDC:2457122,1;2457121,2;2457400,3;2457120,4.展开更多
Enhancing the catalytic activity of catalysts is a core objective in their design and synthesis processes,and the accessibility of active sites is one of the crucial factors determining catalyst activity.Polyoxometala...Enhancing the catalytic activity of catalysts is a core objective in their design and synthesis processes,and the accessibility of active sites is one of the crucial factors determining catalyst activity.Polyoxometalate-based metal-organic complexes(POMOCs)with well-defined structures,which combine the advantages of POMs and MOCs,may offer the possibility to construct catalysts with highly accessible active sites.In this study,a series of POMOCs were successfully designed and synthesized using different POM templates,including[CoII1.5(L)1.5(PMo12O40)(H_(2)O)4]·3H_(2)O(Co-PMo12),[CoII1.5(L)1.5(PW12O40)(H_(2)O)4]·3H_(2)O(Co-PW12),[CoII2(L)2-(SiW12O40)(H_(2)O)4]·11H_(2)O(Co-SiW12),and H[CoII2.5(L)3-(P2W18O62)(H_(2)O)8]·10H_(2)O(Co-P2W18),which were characterized by Fourier transform infrared spectroscopy,powder X-ray diffraction,and single crystal X-ray diffraction.The differences in catalytic activity among the four POMOCs for olefin epoxidation were attributed to the distinct accessibility of Co(II)sites upon thermal activation.Among them,Co-P2W18 achieved a remarkable 99%yield of 1,2-epoxycyclooctane within 3 h at room temperature using O_(2)as the oxidant,owing to its highly accessible unsaturated Co(II)sites.Co-P2W18 exhibits significantly superior catalytic activity for the cyclooctene epoxidation reaction compared to most reported catalysts.Additionally,the reaction mechanism was investigated using density functional theory.展开更多
Charge-transfer complexes(CTCs)have emerged as promising n-type organic thermoelectric(TE)materials due to their inherent high electrical conductivity and tunable transport polarities.In this study,we performed a comp...Charge-transfer complexes(CTCs)have emerged as promising n-type organic thermoelectric(TE)materials due to their inherent high electrical conductivity and tunable transport polarities.In this study,we performed a comprehensive first-principles investigation on the TE properties of nine CTCs comprised of 2,7-dialkyl[1]benzothieno[3,2-b][1]benzothiophenes(CnBTBT,n=4,8,12)as donors and fluorinated derivatives of tetracyanoquinodimethane(F_(m)TCNQ,m=0,2,4)as acceptors,aiming to identify high-performance n-type organic TE materials and elucidate the underlying structure-property relationships.Our calculation results,based on the Boltzmann transport equation and deformation potential theory,reveal that the length of the alkyl side chains and the number of fluorine substitutions significantly impact their electronic structures and TE properties.Notably,the CnBTBT-F_(m)TCNQ CTCs with shorter alkyl chains and more fluorine substitution demonstrate superior n-type characteristics,particularly C4BTBT-F4TCNQ,which achieves an excellent power factor of 671µW cm^(-1) K^(-2) at an optimal charge carrier concentration.Our findings not only clarify the critical role of molecular engineering in CTC-based TE materials but also provide valuable guidance for developing high-efficiency organic TE materials with versatile practical applications.展开更多
A series of blue and blue‑green Ir(Ⅲ)complexes has been investigated theoretically to explore their electronic structures,photophysical properties,efficiency roll‑off effect,and thermal activation delayed fluorescenc...A series of blue and blue‑green Ir(Ⅲ)complexes has been investigated theoretically to explore their electronic structures,photophysical properties,efficiency roll‑off effect,and thermal activation delayed fluorescence(TADF)properties.All calculations were performed using density functional theory(DFT)and time‑dependent density functional theory(TDDFT).Calculations for electronic structures,frontier molecular orbital characteristics(which determine the efficiency roll‑off effect of the complexes),and photophysical properties were conducted using the Gaussian 09 software package.The calculation of spin‑orbit coupling matrix elements<T|HSOC|S>,which determine the TADF properties of the complexes,was performed using the ORCA software package.The calculation results show that the auxiliary ligand tetraphenylimidodiphosphinate(tpip),a strong electron‑withdrawing group,can mitigate the efficiency roll‑off effect of the complex.Furthermore,TADF is observed in one of the designed complexes,(F_(3)Phppy)_(2)Ir(tpip),where F_(3)Phppy=2‑[4‑(2,4,6‑trifluorophenyl)phenyl]pyridine.展开更多
The stability constants of the binary ML2+ and ternary M(ATP)L2? complexes, where L=Iq (isoquinoline) or BIm (benzimidazole) and M=Zn2+ or Cd2+, have been determined by potentiometric pH titration in aqueous solution ...The stability constants of the binary ML2+ and ternary M(ATP)L2? complexes, where L=Iq (isoquinoline) or BIm (benzimidazole) and M=Zn2+ or Cd2+, have been determined by potentiometric pH titration in aqueous solution at I=0.1 mol/L (NaClO4), T=25°C. The stability of the ternary complexes characterized by ΔlogKM=logKM(ATP)LM(ATP)L- logKMML corresponding to the equilibrium M(ATP)2? + ML2+ = M(ATP)L2? + M2+ in higher than what would be expected on statistical grounds. The increase may be related to the stacking interaction between the aromatic ring of the ligands L and the purine moiety of ATP4–. 1H NMR studies of Zn2+/ATP4?/L confirm the presence of stacking in the ternary complexes. It is concluded that the strength of the intramolecular stacking interaction ia dependent on the structure of the aromatic ring of the ligand L and the formation of a metal ion bridge. Possible implications an discussed briefly.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
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
Six lanthanide complexes with bis(phenylsulfinyl)ethane(bphse) and organic bases(phen: 1,10 phenanthroline and bipy: 2,2'-bipyridine) were synthesized and characterized by elemental analysis, conductance and spec...Six lanthanide complexes with bis(phenylsulfinyl)ethane(bphse) and organic bases(phen: 1,10 phenanthroline and bipy: 2,2'-bipyridine) were synthesized and characterized by elemental analysis, conductance and spectral (IR, UV Visible) data. The complexes were Ln(bphse) 2(bipy)(ClO 4) 3· n H 2O and Ln 2(bphse) 3(phen) 2(ClO 4) 6·H 2O(where Ln=Nd, Eu and Gd; n =0～2). IR spectral data confirmed that the lanthanide ions were coordinated by oxygen atoms from bphse and nitrogen atoms from phen or bipy. Exitation and emission spectra of Eu complexes were measured and discussed.展开更多
Four new mixed-ligand complexes of pailadiumt(Ⅱ) with L1(N-benzoyl-α-amino acid dianion) and L2[ethyldiamine (en),2,2’-bipyridine (Bpy) and 1,10-phenanthroline (Phen)] were synthesized.Ail the complexes have been c...Four new mixed-ligand complexes of pailadiumt(Ⅱ) with L1(N-benzoyl-α-amino acid dianion) and L2[ethyldiamine (en),2,2’-bipyridine (Bpy) and 1,10-phenanthroline (Phen)] were synthesized.Ail the complexes have been characterized by elemental analyses,molar conductance,infrared and 1H NMR spectra and therme-gravimetric analyses.Crystal structures of [Pd(Bpy)(Bzval-N,O)] and [Pd(en) (Bzphe-N,O)] H2O have been do termmed by X-ray diffraction analysis.The results indicate that in all the complexes hgand L1 coordinates to palladium (Ⅱ) through deprotonated amide nitrogen and carboxylic oxygen,and there are some intramolecular nonrovalent in teractions in the complexes.展开更多
Synthesizing polyol-based ester from biomass feedstocks for the preparation of biolubricant overcomes the dependence on petroleum oil usage.Albeit biomass-derived bio-oil is an alternative for the production of polyol...Synthesizing polyol-based ester from biomass feedstocks for the preparation of biolubricant overcomes the dependence on petroleum oil usage.Albeit biomass-derived bio-oil is an alternative for the production of polyol ester,upgrading is essential prior to use as biolubricant.Levulinic acid(LA),obtained from bio-oil was applied for the catalytic esterification with two polyols,e.g.,trimethylolpropane(TMP)and pentaerythritol(PE),in the presence of mixed-ligand Ni(Ⅱ),Co(Ⅱ),and Fe(Ⅱ)complexes as catalyst.New mixed-ligand coordination complexes with empirical formula;[Ni(Phe)(Bpy)Cl].H2O,[Co(Phe)(Bpy)Cl].H2O,and[Fe(Phe)(Tyr)Cl].H2O were synthesized by the reaction of ligands[L-phenylalanine(Phe),4,4'-bipyridine(Bpy),and L-tyrosine(Tyr)]with metal chloride salts and characterized by elemental analysis,magnetic susceptibility,FTIR,TGA/DTA,powder-XRD,and SEM techniques.This study aims to investigate the catalytic activities of the complexes via esterification reaction of levulinic acid with trimethylolpropane and pentaerythritol.In addition,these catalysts were further employed for the in situ hydrogenation of levulinate esters via NaBH_(4) at room temperature upon refluxing.Indeed,the iron(Ⅱ)complex was more potential,exhibiting its efficiency as a homogeneous catalyst for esterification-hydrogenation reaction for synthesizing ester-based oils.展开更多
Intracellular bacteria(ICB),cloaked by the protective barriers of host cells,pose a formidable challenge to selective and efficient eradication.The employment of activatable photosensitizers based antibacterial photod...Intracellular bacteria(ICB),cloaked by the protective barriers of host cells,pose a formidable challenge to selective and efficient eradication.The employment of activatable photosensitizers based antibacterial photodynamic therapy(a PDT)holds significant potential for selective imaging and photo-inactivation of ICB while minimizing side effects on normal cells.Drawing inspiration from the elevated hypochlorous acid(HClO)levels in ICB infected phagocytes,herein we firstly designed and synthesized a series of HCl Oresponsive dinuclear Ru(Ⅱ)complexes(Ru1-Ru3)to achieve such a goal.Initially,the luminescence,^(1)O_(2)generation and a PDT activity of these Ru(Ⅱ)complexes were suppressed due to the quenching effect of the azo group,but were recovered after reaction with HCl O in solutions or within ICB infected phagocytes.The detailed results revealed that Ru1 and Ru3 could not only selectively visualize ICB,but also demonstrated remarkable a PDT activity against ICB,surpassing vancomycin both in vitro and in vivo.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
基金This work was supported by the Scientific Research Common Program of Beijing Municipal Commission of Education (KM20051028005)
文摘The mononuclear copper（Ⅱ） complex [Cu（L）（2-AP）] 1 and binuclear copper（Ⅱ） complex [Cu（L）（py）]2 2 （L = C10H11O5NS, taurine o-vanillin, py = prydine, 2-AP = 2-aminopyridine） with mixed ligand have been synthesized and characterized by X-ray diffraction method. Crystal data for 1： orthorhombic, space group Pbca with a = 11.921（4）, b = 15.816（6）, c = 17.076（6） A, V= 3219.7（19） A^3, C15H17CuN3O5S, Z = 8, Mr = 414.92, De = 1.712 g/cm^3,μ（MoKα） = 1.520 mm^-1, F（000） = 1704, the final R = 0.0300 and wR = 0.0705 for 2840 observed reflections with I 〉 2σ（I）; and crystal data for 2： monoclinic, space group P21/c with a = 7.929（3）, b = 17.038（5）, c = 11.734（4） A, β = 98.162（6）°, V = 1569.1（9） A^3, C15H16CuN2O5S, Z = 4, Mr = 399.90, Dc = 1.693 g/cm^3, F（000） = 820,μ（MoKα） = 1.554 mm^-1, the final R = 0.0351 and wR = 0.0848 for 2767 observed reflections （I 〉 2σ（I））. The molecular structure of complex 1 consists of one tetra-coordinated Cu（Ⅱ） atom generating a slightly distorted square plane, and a one-dimensional chain structure is formed by intermolecular hydrogen bonds. Complex 2 consists of a diphenolic hydroxyl O-bridged binuclear copper（Ⅱ） structure. The crystal structures of complexes 1 and 2 reveal that the coordinate copper centers are bound to both nitrogen and oxygen atom donors. The usual N,O-trans arrangement of ligands is observed in both cases.
基金Funded by Key Project of the National Natural Science Foundation of China (No. 60537050)
文摘Two novel mixed-ligand complexes, [M（phen）2（ans）2]·H2O （M = Cd（Ⅱ） 1, Zn（Ⅱ） 2; phen is 1, 10-phenanthroline, and ans is 4-aminonaphthalene-1-sulfonate）, were obtained from the reaction of 1, 10-phenanthroline, sodium 4-aminonaphthalene-1-sulfonate tetrahydrate and acetate in mixed solvents. Interaction of the complexes with calf thymus DNA （ctDNA） were investigated using UV-vis absorption spectra, luminescence titrations, steady-state emission quenching by [Fe（CN）6]4 , DNA competitive binding with ethidium bromide （EB） and viscosity measurements. The experimental results indicate that there exist two interaction modes between the complexes and DNA, namely the electrostatic interaction and intercalation, with the binding constants of 1.82 × 10^5 M-1 for 1 and 4.78 ×10^4 M^- 1 for 2 in buffer of 50 mM NaCl and 5 mM Tris-HCI （pH 7.0）.
文摘Five triboluminescent mixed-ligand complexes of Eu^(3+)with thenoyltrifluoroacetone(TTA)and pyridine-N-oxide or its substitutive derivatives have been prepared.They are all pale yellow crystalline com- pounds with the formula of Eu(TTA)_3·L(L=py NO.2-pie NO,3-pie NO,4-pic NO,bipy N_2O_2).Their physico-chemical properties have been studied with conductometry,UV and IR absorption and fluorescence spectroscopy.Once the complexes are touched or rubbed by a glass rod,they emit strong red triboluminescent light which is similar to the characteristic fluorescence of Eu^(3+).
文摘Three copper(Ⅱ),nickel and cadmium(Ⅱ)complexes,namely[Cu_(2)(μ-H2dbda)2(phen)2]·2H_(2)O(1),[Ni(μ-H2dbda)(μ-bpb)(H_(2)O)2]n(2),and[Cd(μ-H2dbda)(μ-bpa)]n(3),have been constructed hydrothermally using H4dbda(4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid),phen(1,10-phenanthroline),bpb(1,4-bis(pyrid-4-yl)benzene),bpa(bis(4-pyridyl)amine),and copper,nickel and cadmium chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and singlecrystal X-ray diffraction analyses.Single-crystal X-ray diffraction analyses revealed that three complexes crystallize in the monoclinic P21/n,tetragonal I42d,and orthorhombic P21212 space groups.The complexes exhibit molecular dimers(1)or 2D metal-organic networks(2 and 3).The catalytic performances in the Knoevenagel reaction of these complexes were investigated.Complex 1 exhibits an effective catalytic activity and excellent reusability as a heterogeneous catalyst in the Knoevenagel reaction at room temperature.CCDC:2463800,1;2463801,2;2463802,3.
文摘Six new lanthanide complexes:[Ln(3,4-DEOBA)3(4,4'-DM-2,2'-bipy)]2·2C_(2)H_(5)OH,[Ln=Dy(1),Eu(2),Tb(3),Sm(4),Ho(5),Gd(6);3,4-DEOBA-=3,4-diethoxybenzoate,4,4'-DM-2,2'-bipy=4,4'-dimethyl-2,2'-bipyridine]were successfully synthesized by the volatilization of the solution at room temperature.The crystal structures of six complexes were determined by single-crystal X-ray diffraction technology.The results showed that the complexes all have a binuclear structure,and the structures contain free ethanol molecules.Moreover,the coordination number of the central metal of each structural unit is eight.Adjacent structural units interact with each other through hydrogen bonds and further expand to form 1D chain-like and 2D planar structures.After conducting a systematic study on the luminescence properties of complexes 1-4,their emission and excitation spectra were obtained.Experimental results indicated that the fluorescence lifetimes of complexes 2 and 3 were 0.807 and 0.845 ms,respectively.The emission spectral data of complexes 1-4 were imported into the CIE chromaticity coordinate system,and their corre sponding luminescent regions cover the yellow light,red light,green light,and orange-red light bands,respectively.Within the temperature range of 299.15-1300 K,the thermal decomposition processes of the six complexes were comprehensively analyzed by using TG-DSC/FTIR/MS technology.The hypothesis of the gradual loss of ligand groups during the decomposition process was verified by detecting the escaped gas,3D infrared spectroscopy,and ion fragment information detected by mass spectrometry.The specific decomposition path is as follows:firstly,free ethanol molecules and neutral ligands are removed,and finally,acidic ligands are released;the final product is the corresponding metal oxide.CCDC:2430420,1;2430422,2;2430419,3;2430424,4;2430421,5;2430423,6.
文摘Three zinc(Ⅱ),nickel(Ⅱ),and cadmium(Ⅱ)complexes,namely[Zn(μ-Htpta)(py)_(2)]n(1),[Ni(H_(2)biim)2(H_(2)O)2][Ni(tpta)(H_(2)biim)2(H_(2)O)]2·3H_(2)O(2),and[Cd_(3)(μ4-tpta)2(μ-dpe)_(3)]_(n)(3),have been constructed hydrothermally at 160℃ using H_(3)tpta([1,1':3',1″-terphenyl]-4,4',5'-tricarboxylic acid),py(pyridine),H_(2)biim(2,2'-biimidazole),dpe(1,2-di(4-pyridyl)ethylene),and zinc,nickel and cadmium chlorides,resulting in the formation of stable crystalline solids which were subsequently analyzed using infrared spectroscopy,element analysis,thermogravimetric analysis,as well as structural analyses conducted via single-crystal X-ray diffraction.The findings from these single-crystal Xray diffraction studies indicate that complexes 1-3 form crystals within the monoclinic system P2_(1)/c space group(1)or triclinic system P1 space group(2 and 3),and possess 1D,0D,and 3D structures,respectively.Complex 1 demonstrated substantial catalytic efficiency and excellent reusability as a heterogeneous catalyst in the reaction of Knoevenagel condensation under ambient temperature conditions.In addition,complex 1 also showcased notable anti-wear performance when used in polyalphaolefin synthetic lubricants.CCDC:2449810,1;2449811,2;2449812,3.
文摘This paper reports the preparation of three di‑iron complexes containing a thiazole moiety.Esterification of complex[Fe_(2)(CO)_(6)(μ‑SCH_(2)CH(CH_(2)OH)S)](1)with 4‑methylthiazole‑5‑carboxylic acid gave the corresponding ester[Fe_(2)(CO)_(6)(μ‑tedt)](2),where tedt=SCH_(2)CH(CH_(2)OOC(5‑C_(3)HNSCH_(3)))S.Further reactions of complex 2 with tri(ptolyl)phosphine(tp)or tris(4‑fluorophenyl)phosphine(fp)gave the phosphine‑substituted derivatives[Fe_(2)(CO)_(5)(tp)(μ‑tedt)](3)and[Fe_(2)(CO)_(5)(fp)(μ‑tedt)](4).The structures of the newly prepared complexes were elucidated by elemental analysis,NMR,IR,and X‑ray photoelectron spectroscopy.Moreover,single‑crystal X‑ray diffraction analysis confirmed their molecular structures,showing that they contain a di‑iron core ligated by a bridged dithiolate bearing a thiazole moiety and terminal carbonyls.The electrochemical and electrocatalytic proton reduction were probed by cyclic voltammetry,revealing that three complexes can catalyze the reduction of protons to H_(2) under the electrochemical conditions.For comparison,complex 4 possessed the best efficiency with a turnover frequency of 23.5 s^(-1)at 10 mmol·L^(-1)HOAc concentration.In addition,the fungicidal activity of these complexes was also investigated in this study.CCDC:2477511,2;2477512,3;2477513,4.
基金supported by the National Natural Science Foundation of China(22025503,22220102004,22401093)the Science and Technology Commission of Shanghai Municipality(24DX1400200)+2 种基金the Innovation Program of Shanghai Municipal Education Commission(2023ZKZD40)the Programme of Introducing Talents of Discipline to Universities(B16017)the China Postdoctoral Science Foundation(2023M741167,GZB20230211,2024T170273)。
文摘While biomaterials are endowed with sophisticated functions by the temporal dynamics and autonomy derived from non-equilibrium assemblies in biological systems,fabricating advanced materials counterparts with these features through kinetic control remains rare.Herein,we report a non-equilibrium hydrogel that exhibits autonomous time-dependent ultrabright fluorescence(quantum yield 0.90),achieved through the kinetically controlled incorporation of thermodynamic equilibrium host-vip complexes into a poly(2-hydroxyethyl methacrylate)(PHEMA)network.Transient complexes are programmed by coupling rapid assembly kinetics with the slow competitive binding of the polymer matrix.This kinetic mismatch converts a thermodynamic equilibrium supramolecular system into a non-equilibrium state,generating temporally dynamic fluorescence that cyclically shifts from yellow to green and self-reverts.The programmed temporal dynamics endow the hydrogel with high potential for information encryption applications.
文摘The complexes 1-4 of cyclobutanocucurbit[5]uril(CyB5Q[5])with Na^(+)/K^(+)have been synthesized and characterized by single-crystal X-ray diffraction.The results show that although the inorganic salts are used when the cations are the same and the anions are different,in complex 1,Na^(+)closes one port of CyB5Q[5]through Na—O seven coordination bonds to form a molecular bowl;in complex 3,Na^(+)completely closes the two ports of CyB5Q[5]to form a molecular capsule with six Na—O coordination bonds;in complexes 2 and 4,the two ports of CyB5Q[5]are completely closed to form K—O coordinated molecular capsules,but the K^(+)of complex 2 is six-coordinated and that of complex 4 is eight-/nine-coordinated.and complex 4 are connected by three oxygen bridges to form a 1D molecular chain.CCDC:2457122,1;2457121,2;2457400,3;2457120,4.
基金financially supported by the National Natural Science Foundation of China(22271021,21971024,and 22201021)the Natural Science Foundation and Education Department of Liaoning Province(LJ232410167011)。
文摘Enhancing the catalytic activity of catalysts is a core objective in their design and synthesis processes,and the accessibility of active sites is one of the crucial factors determining catalyst activity.Polyoxometalate-based metal-organic complexes(POMOCs)with well-defined structures,which combine the advantages of POMs and MOCs,may offer the possibility to construct catalysts with highly accessible active sites.In this study,a series of POMOCs were successfully designed and synthesized using different POM templates,including[CoII1.5(L)1.5(PMo12O40)(H_(2)O)4]·3H_(2)O(Co-PMo12),[CoII1.5(L)1.5(PW12O40)(H_(2)O)4]·3H_(2)O(Co-PW12),[CoII2(L)2-(SiW12O40)(H_(2)O)4]·11H_(2)O(Co-SiW12),and H[CoII2.5(L)3-(P2W18O62)(H_(2)O)8]·10H_(2)O(Co-P2W18),which were characterized by Fourier transform infrared spectroscopy,powder X-ray diffraction,and single crystal X-ray diffraction.The differences in catalytic activity among the four POMOCs for olefin epoxidation were attributed to the distinct accessibility of Co(II)sites upon thermal activation.Among them,Co-P2W18 achieved a remarkable 99%yield of 1,2-epoxycyclooctane within 3 h at room temperature using O_(2)as the oxidant,owing to its highly accessible unsaturated Co(II)sites.Co-P2W18 exhibits significantly superior catalytic activity for the cyclooctene epoxidation reaction compared to most reported catalysts.Additionally,the reaction mechanism was investigated using density functional theory.
基金supported by the Strategic Priority Research Program of the Chinese Academy of Science(No.XDB0520000)the National Natural Science Foundation of China(Nos.52273170 and 52394271)the National Key R&D Program of China(No.2022YFA1203200).
文摘Charge-transfer complexes(CTCs)have emerged as promising n-type organic thermoelectric(TE)materials due to their inherent high electrical conductivity and tunable transport polarities.In this study,we performed a comprehensive first-principles investigation on the TE properties of nine CTCs comprised of 2,7-dialkyl[1]benzothieno[3,2-b][1]benzothiophenes(CnBTBT,n=4,8,12)as donors and fluorinated derivatives of tetracyanoquinodimethane(F_(m)TCNQ,m=0,2,4)as acceptors,aiming to identify high-performance n-type organic TE materials and elucidate the underlying structure-property relationships.Our calculation results,based on the Boltzmann transport equation and deformation potential theory,reveal that the length of the alkyl side chains and the number of fluorine substitutions significantly impact their electronic structures and TE properties.Notably,the CnBTBT-F_(m)TCNQ CTCs with shorter alkyl chains and more fluorine substitution demonstrate superior n-type characteristics,particularly C4BTBT-F4TCNQ,which achieves an excellent power factor of 671µW cm^(-1) K^(-2) at an optimal charge carrier concentration.Our findings not only clarify the critical role of molecular engineering in CTC-based TE materials but also provide valuable guidance for developing high-efficiency organic TE materials with versatile practical applications.
文摘A series of blue and blue‑green Ir(Ⅲ)complexes has been investigated theoretically to explore their electronic structures,photophysical properties,efficiency roll‑off effect,and thermal activation delayed fluorescence(TADF)properties.All calculations were performed using density functional theory(DFT)and time‑dependent density functional theory(TDDFT).Calculations for electronic structures,frontier molecular orbital characteristics(which determine the efficiency roll‑off effect of the complexes),and photophysical properties were conducted using the Gaussian 09 software package.The calculation of spin‑orbit coupling matrix elements<T|HSOC|S>,which determine the TADF properties of the complexes,was performed using the ORCA software package.The calculation results show that the auxiliary ligand tetraphenylimidodiphosphinate(tpip),a strong electron‑withdrawing group,can mitigate the efficiency roll‑off effect of the complex.Furthermore,TADF is observed in one of the designed complexes,(F_(3)Phppy)_(2)Ir(tpip),where F_(3)Phppy=2‑[4‑(2,4,6‑trifluorophenyl)phenyl]pyridine.
基金Project (No.29170038) supported by the National Natural Science Foundation of China。
文摘The stability constants of the binary ML2+ and ternary M(ATP)L2? complexes, where L=Iq (isoquinoline) or BIm (benzimidazole) and M=Zn2+ or Cd2+, have been determined by potentiometric pH titration in aqueous solution at I=0.1 mol/L (NaClO4), T=25°C. The stability of the ternary complexes characterized by ΔlogKM=logKM(ATP)LM(ATP)L- logKMML corresponding to the equilibrium M(ATP)2? + ML2+ = M(ATP)L2? + M2+ in higher than what would be expected on statistical grounds. The increase may be related to the stacking interaction between the aromatic ring of the ligands L and the purine moiety of ATP4–. 1H NMR studies of Zn2+/ATP4?/L confirm the presence of stacking in the ternary complexes. It is concluded that the strength of the intramolecular stacking interaction ia dependent on the structure of the aromatic ring of the ligand L and the formation of a metal ion bridge. Possible implications an discussed briefly.
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.
文摘Six lanthanide complexes with bis(phenylsulfinyl)ethane(bphse) and organic bases(phen: 1,10 phenanthroline and bipy: 2,2'-bipyridine) were synthesized and characterized by elemental analysis, conductance and spectral (IR, UV Visible) data. The complexes were Ln(bphse) 2(bipy)(ClO 4) 3· n H 2O and Ln 2(bphse) 3(phen) 2(ClO 4) 6·H 2O(where Ln=Nd, Eu and Gd; n =0～2). IR spectral data confirmed that the lanthanide ions were coordinated by oxygen atoms from bphse and nitrogen atoms from phen or bipy. Exitation and emission spectra of Eu complexes were measured and discussed.
基金Project supported by the Natural Science Foundation of Zhejiang ProvinceChina
文摘Four new mixed-ligand complexes of pailadiumt(Ⅱ) with L1(N-benzoyl-α-amino acid dianion) and L2[ethyldiamine (en),2,2’-bipyridine (Bpy) and 1,10-phenanthroline (Phen)] were synthesized.Ail the complexes have been characterized by elemental analyses,molar conductance,infrared and 1H NMR spectra and therme-gravimetric analyses.Crystal structures of [Pd(Bpy)(Bzval-N,O)] and [Pd(en) (Bzphe-N,O)] H2O have been do termmed by X-ray diffraction analysis.The results indicate that in all the complexes hgand L1 coordinates to palladium (Ⅱ) through deprotonated amide nitrogen and carboxylic oxygen,and there are some intramolecular nonrovalent in teractions in the complexes.
基金financial support from Universiti Malaya(Grand Challenge(Innovative Technology(ITRC)(GC001B-14AET)),RU Geran(ST012-2018)Postgraduate(Research Grant(PPP,Project number:PG250-2016A)).
文摘Synthesizing polyol-based ester from biomass feedstocks for the preparation of biolubricant overcomes the dependence on petroleum oil usage.Albeit biomass-derived bio-oil is an alternative for the production of polyol ester,upgrading is essential prior to use as biolubricant.Levulinic acid(LA),obtained from bio-oil was applied for the catalytic esterification with two polyols,e.g.,trimethylolpropane(TMP)and pentaerythritol(PE),in the presence of mixed-ligand Ni(Ⅱ),Co(Ⅱ),and Fe(Ⅱ)complexes as catalyst.New mixed-ligand coordination complexes with empirical formula;[Ni(Phe)(Bpy)Cl].H2O,[Co(Phe)(Bpy)Cl].H2O,and[Fe(Phe)(Tyr)Cl].H2O were synthesized by the reaction of ligands[L-phenylalanine(Phe),4,4'-bipyridine(Bpy),and L-tyrosine(Tyr)]with metal chloride salts and characterized by elemental analysis,magnetic susceptibility,FTIR,TGA/DTA,powder-XRD,and SEM techniques.This study aims to investigate the catalytic activities of the complexes via esterification reaction of levulinic acid with trimethylolpropane and pentaerythritol.In addition,these catalysts were further employed for the in situ hydrogenation of levulinate esters via NaBH_(4) at room temperature upon refluxing.Indeed,the iron(Ⅱ)complex was more potential,exhibiting its efficiency as a homogeneous catalyst for esterification-hydrogenation reaction for synthesizing ester-based oils.
基金supported by National Natural Science Foundation of China(No.22371289)。
文摘Intracellular bacteria(ICB),cloaked by the protective barriers of host cells,pose a formidable challenge to selective and efficient eradication.The employment of activatable photosensitizers based antibacterial photodynamic therapy(a PDT)holds significant potential for selective imaging and photo-inactivation of ICB while minimizing side effects on normal cells.Drawing inspiration from the elevated hypochlorous acid(HClO)levels in ICB infected phagocytes,herein we firstly designed and synthesized a series of HCl Oresponsive dinuclear Ru(Ⅱ)complexes(Ru1-Ru3)to achieve such a goal.Initially,the luminescence,^(1)O_(2)generation and a PDT activity of these Ru(Ⅱ)complexes were suppressed due to the quenching effect of the azo group,but were recovered after reaction with HCl O in solutions or within ICB infected phagocytes.The detailed results revealed that Ru1 and Ru3 could not only selectively visualize ICB,but also demonstrated remarkable a PDT activity against ICB,surpassing vancomycin both in vitro and in vivo.
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.
