Photoluminescent hybrid materials containing carboxymethyl cellulose and lanthanide ions（Eu3＋, Tb3＋）were prepared by a facile method under ambient conditions. Lanthanide ions were covalently grafted to the cellulo...Photoluminescent hybrid materials containing carboxymethyl cellulose and lanthanide ions（Eu3＋, Tb3＋）were prepared by a facile method under ambient conditions. Lanthanide ions were covalently grafted to the cellulose framework through coordination with the carboxylic groups of the cellulose. Hybrid materials were fabricated as hydrogel and aerogel. As shown by SEM and pore parameters, aerogel materials which were obtained by supercritical CO2 drying show hierarchical porous structure. The photoluminescence spectrum of the hybrid materials shows the characteristic red emission of Eu3＋ ion and green emission of Tb3＋. Further luminescent investigations reveal that these hybrid materials can detect Fe3＋ with relative selectivity and high sensitivity, which suggests that the hybrid materials could be a promising luminescent probe for selectively sensing Fe3＋ ion.展开更多
Sensing of analyte s in biological fluids and biotechnological production media remains a challenge.He re,the luminescent response of the europium(Ⅲ)complex of 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid(DO3A...Sensing of analyte s in biological fluids and biotechnological production media remains a challenge.He re,the luminescent response of the europium(Ⅲ)complex of 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid(DO3A)to bicarbonate was investigated in detail.The response of Eu.DO3A to changes in bicarbonate concentration was studied in different buffers,and the influence of ionic strength,pH,and specific ions was determined.The response is found to depend on pH and ionic strength,but it is not possible to separate contributions from the sensing event from those in the bicarbonate activity.Prior to demonstrating the ability to determine the bicarbonate concentration in bioproduction media and serum,the influence of competing carboxy anions was evaluated.It is established that while competing anions bind stronger to the responsive complex,at the relevant concentration their contribution to the recorded signal is negligible.We are thus able to conclude that Eu.DO3A is a good platform for building a bicarbonate sensor.展开更多
A new complex, {[Cd（BIDPT）（NBA）]}n（1）, was synthesized from the selfassembly of BIDPT（BIDPT = 4,4?-bis（imidazol-l-yl）diphenyl thioether） and H2NBA（H2 NBA = 4,4?-azanediyldibenzoic acid） ligands with Cd（Ⅱ...A new complex, {[Cd（BIDPT）（NBA）]}n（1）, was synthesized from the selfassembly of BIDPT（BIDPT = 4,4?-bis（imidazol-l-yl）diphenyl thioether） and H2NBA（H2 NBA = 4,4?-azanediyldibenzoic acid） ligands with Cd（Ⅱ）. 1 was characterized by infrared spectroscopy, powder X-ray diffraction, elemental analysis, and thermogravimetry measurement. 1 crystallizes in monoclinic system, space group P21/c with a = 8.8204（1）, b = 29.835（3）, c = 10.3813（1） ?, β = 96.180（2）°, V = 2730.7（5） ?3, Z = 4, C32H22CdN5O4S, Mr = 685.01, Dc = 1.666 g/cm3, μ = 0.926 mm-1, R = 0.0548 and wR = 0.1528. 1 features a parallel structure with 3-connected hcb network and the adjacent 2 D networks are stacked together via C–H···π interaction to form a 3 D network. Its application in detecting metal cations and inorganic anions was explored. 1 exhibits excellent photoluminescence sensing for Fe3+ and Cr2O72- ions. And the mechanism of quenching is also studied.展开更多
A novel coordination polymer Zn(DMA)(TBA)(1)(H_(2)TBA=4-(1H-tetrazol-5-yl)-benzoic acid)features a unique two-dimensional(2D)network structure,exhibiting excellent luminescence and good stability in both water and oth...A novel coordination polymer Zn(DMA)(TBA)(1)(H_(2)TBA=4-(1H-tetrazol-5-yl)-benzoic acid)features a unique two-dimensional(2D)network structure,exhibiting excellent luminescence and good stability in both water and other organic solvents.1 shows excellent selectivity.展开更多
N-Methylformamide(NMF)has been recognized as one of the most important industrially relevant solvents and a crucial intermediate used in industrial processes.However,indiscriminate use of NMF has been perceived as a t...N-Methylformamide(NMF)has been recognized as one of the most important industrially relevant solvents and a crucial intermediate used in industrial processes.However,indiscriminate use of NMF has been perceived as a threat to sustainable development owing to the lack of effective monitoring.In this study,a bimetallic lanthanide metal–organic framework(LMOF)with a fast response time and high sensitivity for monitoring of NMF is designed and fabricated,which also exhibits strong fluorescence.The response emission signals toward NMF range from red to green and are significantly correlated with the increase in the solvent concentration of NMF.Considering the fast response and excellent sensitivity results,a logic gate with AND functions for NMF is constructed.展开更多
In order to reduce usage cost and simplify the detection process,it is necessary to develop multifunc-tional and multi-emitter Ln-MOF luminescent sensors.The structure and property of Ln-MOFs are mainly controlled by ...In order to reduce usage cost and simplify the detection process,it is necessary to develop multifunc-tional and multi-emitter Ln-MOF luminescent sensors.The structure and property of Ln-MOFs are mainly controlled by ligands.As a typical aromatic nucleus,naphthalene groups not only can emit fluorescence and regulate the energy levels of a ligand but also can participate inπ-πstacking.As a type of directional weak interaction,hydrogen bonding interactions have caught wide attention in catalysis,molecular reco-gnition,self-assembly,etc.So we designed a“V”shaped ligand containing naphthalene groups and“O■C-NH”groups as guided by DFT calculations.The obtained Eu-MOF can achieve simultaneous luminescence of the ligand and Eu^(3+).Single crystal X-ray diffraction revealed thatπ-πstacking inter-actions and hydrogen bonding interactions played an important role in the crystallization process.The luminescence spectra showed that the Eu-MOF has two luminescent centers and can be developed as a ratiometric luminescent sensor.The luminescence of the Eu-MOF can undergo an obvious color change from red to white as the temperature rises from 120 to 400 K and the Eu-MOF has a satisfactory relative sensitivity and a small temperature uncertainty.Moreover,the Eu-MOF can detect picric acid selectively and the K_(SV) can reach 53339 M^(−1).Thus,the Eu-MOF can be used as a multifunctional and multi-emitter luminescent sensor and the designed strategy also can provide inspiration for further research on Eu-MOFs.展开更多
Five isostructural lanthanide metal–organic frameworks [Ln(BDPO)(H_(2)O)_(4)] (Ln = Eu for CUST-623, Tb for CUST-624, Gd for CUST-625, Dy for CUST-626, and Sm for CUST-627, BDPO = N,N'-bis(3,5-dicarboxyphenyl)-ox...Five isostructural lanthanide metal–organic frameworks [Ln(BDPO)(H_(2)O)_(4)] (Ln = Eu for CUST-623, Tb for CUST-624, Gd for CUST-625, Dy for CUST-626, and Sm for CUST-627, BDPO = N,N'-bis(3,5-dicarboxyphenyl)-oxalamide) were synthesized by the solvothermal method. Single-crystal X-ray diffraction shows that Ln-MOFs manifest framework structures with two kinds of 1D open channels in the b-axis direction. Dual emission luminescent thermometer films were successfully prepared by immobilizing Eu_(x)Tb_(0.02−x)-BDPO into polyvinyl alcohol (PVA) aqueous solution, which features the integrity of MOF powders, proving their excellent processability. Moreover, Eu0.002Tb0.018-BDPO@PVA shows excellent temperature sensing performance with a high sensitivity of 3.7% K^(−1) in the temperature range of 303 K–423 K. CUST-623 and CUST-624 can be used as multiresponse fluorescent sensors for detecting Fe^(3+), Cr_(2)O_(7)^(2−), CrO_(4)^(2−) and TNP. In addition, the mechanism of fluorescence sensing is investigated by infrared (IR) spectroscopy, powder X-ray diffraction (PXRD) and ultraviolet–visible (UV-vis) spectroscopy. This work provides a general method for constructing Ln-MOF sensor materials with multifunctional luminescence characteristics.展开更多
The fast,sensitive and selective detection of some antibiotics and heavy metal cations in water is highly desirable for environmental protection and human health,but it is still currently challenging.In this work,a ne...The fast,sensitive and selective detection of some antibiotics and heavy metal cations in water is highly desirable for environmental protection and human health,but it is still currently challenging.In this work,a new luminescent Eu(Ⅲ)-based metalorganic framework(MOF),{[(CH_(3))_(2)NH_(2)][Eu(L)2(H_(2)O)_(2)]·xDMF}n(1)[H_(2)L=4,4’-((naphthalene-1,4-dicarbonyl)bis(azanediyl))dibenzoic acid],was solvothermally synthesized.Complex 1 exhibits good water stability and luminescent property and could serve as a bifunctional ratiometric luminescent sensor for fast,sensitive and selective detection of ornidazole(ODZ)and Hg^(2+)in aqueous solution.The corresponding luminescent mechanism has also been discussed.This work indicates that 1 as a promising luminescent material exhibits luminescent quenching behavior for ODZ and luminescent enhancement behavior for Hg^(2+)in H_(2)O,which will promote the practical application of Ln-MOF-based ratiometric luminescent sensors in monitoring antibiotics and metal ions pollutants in the environmental water matrices.展开更多
The platinum(II) terpyridyl acetylide complex [Pt(terpy)(C≡CR)]ClO4 (terpy=2,2'∶6'2''-terpyridine, R=CH2CH2CH3) (1) was incorporated into Nafion membranes. At high loading the dry membranes exhibit i...The platinum(II) terpyridyl acetylide complex [Pt(terpy)(C≡CR)]ClO4 (terpy=2,2'∶6'2''-terpyridine, R=CH2CH2CH3) (1) was incorporated into Nafion membranes. At high loading the dry membranes exhibit intense photoluminescence with max at 707 nm from the 3MMLCT state, which was not observed in fluid solution. Upon exposure to the vapor of polar volatile organic compounds (VOC), this photoluminescence was significantly red-shifed. This process was fully reversible when the VOC-incorporated membrane was dried in air. The dramatic and reversible changes in the emission spectra made the Nafion-supported complex as an interesting sensor candi-date for polar VOC.展开更多
A dual colorimetric and luminescent sensor based on a heteroleptic ruthenium dye [Ru（Hipdpa）（Hdcb- py）（NCS）2]^-.0.5H^＋ 0.5[N（C4H9）4]＋ Ru（Hipdpa） {where Hdcbpy = monodeprotonted-4,4＇-dicarboxy-2,2＇- bipyr...A dual colorimetric and luminescent sensor based on a heteroleptic ruthenium dye [Ru（Hipdpa）（Hdcb- py）（NCS）2]^-.0.5H^＋ 0.5[N（C4H9）4]＋ Ru（Hipdpa） {where Hdcbpy = monodeprotonted-4,4＇-dicarboxy-2,2＇- bipyridine and Hipdpa = 4-（1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl）-N,N-diphenylaniline} for selective detection of Hg2. is presented. The results of spectrophotometric titrations revealed an evident luminescence intensity enhancement （I/Io = 11 ） and a considerable blue shift in visible absorption and luminescence maxima with the addition of rig2.. The sensitive response of the optical sensor on Hg^2＋ was attributed to the binding of the electron-deficient Hg^2＋ to the electron-rich sulfur atom of the thiocyanate （NCS） ligand in the Ru（Hipdpa）, which led to an increase in the energy gap between the highest occupied molecular orbital （HOMO） and the lowest unoccupied molecular orbital （LUMO）. Accordingly, the blue shift in the absorption spectrum of Ru（Hipdpa） due to the binding of Hg2. was obtained. Ru（Hipdpa） was found to have decreased Hg2~ detection limit and improved linear region as compared to di（tetrabutylammonium） cis-bis（isothiocyanato）bis（2,2＇-bipyridine-4-carboxylic acid-4＇- carboxylate）ruthenium（ll） N719. Moreover, a dramatic color change from pink to yellow was observed, which allowed simple monitoring of Hg^2＋ by either naked eyes or a simple colorimetric reader. Therefore, the proposed sensor can provide potential applications for Hg2＊ detection.展开更多
Detecting hazardous hydrogen halides(HX,X=Cl,Br,and I)gas is critical for human health and ecological safety.A luminescent sensor based on anion exchange reaction(AER)in perovskite could offer a cost-effective approac...Detecting hazardous hydrogen halides(HX,X=Cl,Br,and I)gas is critical for human health and ecological safety.A luminescent sensor based on anion exchange reaction(AER)in perovskite could offer a cost-effective approach.However,resolving the challenging issues of instability and the acceleration requirement of AER is highly desired for practical applications.Here,we develop an ultra-rapid,sensitive,and reusable HCl luminescent gas sensor through nanoconfining MAPbBr3 quantum dots(QDs)into a transparent nanoporous glass(NG)matrix,successfully extending perovskite glass to the organic-inorganic system,which exhibits enhanced AER sensitivity.Utilizing enhanced transport efficiency of reactants within NG,HCl gas could be rapidly adsorbed into the nanopores and undergo ultra-rapid AER with the embedded perovskite QDs.In addition,the device stability could be fostered by the physical protection of glass matrix.After being simply integrated with UV LED,the MAPbBr3-NG exhibits an ultra-rapid response time within 2 s at a HCl gas concentration of 5 ppm.Furthermore,this luminescent gas sensor demonstrates robust performance,retaining functionality over 10 reuse cycles.This compact,cost-effective,and highly sensitive device with rapid response capability could open a promising avenue for research on HX detection while expanding the practical applications of perovskite-based devices.展开更多
Chiral recognition,particularly the recognition of different enantiomers of chiral drugs,is important for human life and health safety.Here,we designed a two-dimensional(2D)confined polyoxometalate-based chiral lumine...Chiral recognition,particularly the recognition of different enantiomers of chiral drugs,is important for human life and health safety.Here,we designed a two-dimensional(2D)confined polyoxometalate-based chiral luminescence sensor by encapsulating luminescent[EuW_(10)O_(36)]^(9-)clusters(EuW_(10))within the chiral 2D interlayer of layered double hydroxides modified with chiral ionic liquids(L-CIL-Mg_(3)Al-EuW_(10)).展开更多
The abuse of antibiotics has brought great harm to the human living environment and health,so it is extremely significant to develop an efficient and simple method to detect trace antibiotic residues in various wastew...The abuse of antibiotics has brought great harm to the human living environment and health,so it is extremely significant to develop an efficient and simple method to detect trace antibiotic residues in various wastewaters.Herein,a new two-dimensional(2D)Cd-based metal−organic framework(Cd-MOF,namely LCU-111)and its mixed matrix membranes(MMMs)is sifted as luminescence sensors for efficient monitoring antibiotic nitrofurazone(NFZ)in various aqueous systems and applied as visible fingerprint identifying.The LCU-111 has good selectivity,sensibility,reproducibility and anti-interference for luminescent quenching NFZ with low detection limits(LODs)of 0.4567,0.3649 and 0.8071 ppm in aqueous solution,HEPES biological buffer,and real urban Tuhai River water,respectively.Interestingly,the luminescent test papers and MMMs allow the NFZ sensing easier and more rapid by naked eyes,only with a low LOD of 0.8117 ppm for MMMs sensor.Notably,by combining multiple experiments with density functional theory(DFT)calculations,the photo-induced electron transfer(PET)quenching mechanism is further elucidated.More importantly,potential practical applications of LCU-111 for latent fingerprint visualization provide lifelike evidences for effective identification of individuals,which can be applied in criminal investigation.展开更多
Various ions and antibiotics,widely used in industry and clinical medicine,respectively,are massively discharged to atmosphere and water,resulting in severe pollutions on environment and potential threats to human hea...Various ions and antibiotics,widely used in industry and clinical medicine,respectively,are massively discharged to atmosphere and water,resulting in severe pollutions on environment and potential threats to human health.Besides,amino acids,the primary substances for the establishment of proteins,cells and tissues,are crucial to human health.Therefore,seeking effective and practicable materials to detect aforesaid analytes is vitally meaningful.Metal-organic frameworks centered with lanthanide ions(Ln-MOFs),also known as lanthanide coordination polymers,are considered as a charming category of multi-functional hybrid crystalline materials with fascinating structures and incomparable luminescent characteristics.Benefited from their unique merits,Ln-MOFs have been largely developed as excellent luminescent sensors for fast and efficient sensing various analytes.In this review,we aim to introduce some of the recent researches between 2018 to 2022 on Ln-MOFs applied as chemical sensors for ions,antibiotics and amino acids based on luminescent quenching and enhancing effects,and provide an update and summary for the latest progresses in this field.展开更多
Gold nanoclusters(Au NCs)are promising luminescent nanomaterials due to their outstanding optical properties.However,their relatively low quantum yields and environment-dependent photoluminescence properties have limi...Gold nanoclusters(Au NCs)are promising luminescent nanomaterials due to their outstanding optical properties.However,their relatively low quantum yields and environment-dependent photoluminescence properties have limited their biological applications.To address these problems,we developed a novel strategy to prepare chitosan oligosaccharide lactate(Chi)-functionalized Au NCs(Au NCs@Chi),which exhibited emission with enhanced quantum yield and elongated emission lifetime as compared to the Au NCs,as well as exhibited environment-independent photoluminescence properties.In addition,utilizing the free amino groups of Chi onto Au NCs@Chi,we designed a FRET-based sensing platform for the detection of hydrogen sulfide(H_(2)S).The Au NCs and the specific H_(2)S-sensitive merocyanine compound were respectively employed as an energy donor and acceptor in the platform.The addition of H_(2)S induced changes in the emission profile and luminescence lifetime of the platform with high sensitivity and selectivity.Utilization of the platform was demonstrated to detect exogenous and endogenous H_(2)S in vitro and in vivo through wavelength-ratiometric and time-resolved luminescence imaging(TLI).Compared to previously reported luminescent molecules,the platform was less affected by experimental conditions and showed minimized autofluorescence interference and improved accuracy of detection.展开更多
Two porous organic polymer nanotubes(PNT-2 and PNT-3) were synthesized via Ni-catalyzed Yamamoto reaction, using2,4,6-tris-(4-bromo-phenyl)-[1,3,5]-triazine(TBT) as one monomer, and 2,7-dibromopyrene(DBP) or 1,3,6,8-t...Two porous organic polymer nanotubes(PNT-2 and PNT-3) were synthesized via Ni-catalyzed Yamamoto reaction, using2,4,6-tris-(4-bromo-phenyl)-[1,3,5]-triazine(TBT) as one monomer, and 2,7-dibromopyrene(DBP) or 1,3,6,8-tetrabromopyrene(TBP) as another monomer. The scanning electron microscope(SEM) images show that both PNT-2 and PNT-3 possess clear hollow tube structures. Luminescent measurements indicate that both PNT-2 and PNT-3 can serve as luminescent probe for highly selective and sensitive detection of Fe^(3+) by luminescent quenching effect. Absorption competition quenching(ACQ) mechanism is also proposed to explain luminescent quenching behavior, i.e., the overlap of the UV-spectra between Fe^(3+) and PNTs causes the energy competition, and therefore leads to luminescent quenching. Moreover, both PNT-2 and PNT-3 still show high selectivity and sensitivity for sensing Fe^(3+) in 10% ethanol aqueous solution, which means that the two porous PNTs are promising candidates as luminescent probes for detecting Fe^(3+) in practical applications.展开更多
Perfluorooctanoic acid(PFOA),a persistent environmental pollutant,poses serious health risks and remains challenging to detect due to its low light absorption and weak binding affinity.Luminescence sensing offers a po...Perfluorooctanoic acid(PFOA),a persistent environmental pollutant,poses serious health risks and remains challenging to detect due to its low light absorption and weak binding affinity.Luminescence sensing offers a powerful approach to its rapid and quantitative detection,with electron transfer playing a critical role when energy transfer is limited by the analyte’s unfavorable energy-level alignment.Lanthanidebased metal–organic frameworks(MOFs),featuring sharp emissions,long-lived excited states,and tunable electronic structures,are particularly promising for such applications owing to their ability to precisely regulate electron transfer pathways through structural modulation.However,the impact of the coordination mode and symmetry on sensing performance remains poorly understood due to its complex mechanisms.Herein,we report a series of eight europiumbased MOFs,Eu_(2)(FDA)_(3)(solvent)x,synthesized using a single ligand to enable systematic investigation of the relationship between Eu^(3+) coordination symmetry and PFOA sensing behavior.Notably,MOFs with lower coordination symmetry exhibit significantly higher quenching efficiency due to increased energy-level splitting that promotes electron transfer.This study establishes a clear structurefunction correlation and provides valuable insights for the rational design of MOF-based sensors targeting spectroscopically challenging contaminants,thereby deepening the understanding of luminescence sensing mechanisms based on structure-driven signal transduction processes.展开更多
Open metal sites(OMSs)represent a distinctive feature of metal-organic frameworks(MOFs),intertwined with vip accommodation and energy transfer within nanosized pores.Fine-tuning OMSs provide an effective approach to...Open metal sites(OMSs)represent a distinctive feature of metal-organic frameworks(MOFs),intertwined with vip accommodation and energy transfer within nanosized pores.Fine-tuning OMSs provide an effective approach to regulating MOF’s responsiveness and binding affinity towards vips,allowing for the construction of luminescent sensors for specific analytes.Such a strategy remains unexplored due to the inherent complexity of the systems and sensing mechanisms.Herein,we delicately regulated the OMSs in PCN-700 through multiple synthetic methodologies,including direct synthesis,linker installation,and linker exchange.The resultant MOFs consist of Zr6-clusters featuring various coordination numbers.Notably,PCN-700-8u with unsaturated 8-coordinated Zr-clusters exhibited the highest sensitivity in detecting a toxic pesticide pentachloronitrobenzene(PCNB)due to the presence of strong coordination interaction,as validated through single crystal X-ray diffraction directly.PCN-700-10u/12u bearing unsaturated 10/12-coordinated clusters perform lower quenching efficiencies than PCN-700-8u,but higher than PCN-700-12s with saturated clusters.In contrast,all these MOFs exhibit similar quenching efficiencies towards hexachlorobenzene for the absence of coordination interaction.This study not only develops a cost-effective and easily attainable material for PCNB detection,but also illuminates the pivotal importance of OMSs in customizing MOF-based sensors for practical applications.展开更多
The aluminum based MOFs compound, MIL-96(Al), has been studied as a luminescence sensor by incorporating of Eu3+ ions, which renders the compound strong red-light emission. The as-synthesized MIL-96(Al):Eu3+ nanocryst...The aluminum based MOFs compound, MIL-96(Al), has been studied as a luminescence sensor by incorporating of Eu3+ ions, which renders the compound strong red-light emission. The as-synthesized MIL-96(Al):Eu3+ nanocrystals exhibit water dispersibility and environmental stability, which are general requirement for an ideal sensing material. The MIL-96(Al):Eu3+ nanocrystals show excellent selective detection ability on Fe3+ ions in aqueous solution with value of low detection limit 20 μM. Meanwhile, it also exhibits excellent selective detection ability on CrO42- and Cr2O72- in aqueous solution with value of low detection limit 10 and 22 μM, respectively. The results of this study show that MIL-96(Al):Eu3+ nanocrystals could be used as a multi-responsive luminescent senor for Fe3+ and Cr(Ⅵ) species in aqueous solution. The possible luminescence quenching mechanism has also been discussed.展开更多
基金Project supported by the National Natural Science Foundation of China(21161023,21661034)
文摘Photoluminescent hybrid materials containing carboxymethyl cellulose and lanthanide ions（Eu3＋, Tb3＋）were prepared by a facile method under ambient conditions. Lanthanide ions were covalently grafted to the cellulose framework through coordination with the carboxylic groups of the cellulose. Hybrid materials were fabricated as hydrogel and aerogel. As shown by SEM and pore parameters, aerogel materials which were obtained by supercritical CO2 drying show hierarchical porous structure. The photoluminescence spectrum of the hybrid materials shows the characteristic red emission of Eu3＋ ion and green emission of Tb3＋. Further luminescent investigations reveal that these hybrid materials can detect Fe3＋ with relative selectivity and high sensitivity, which suggests that the hybrid materials could be a promising luminescent probe for selectively sensing Fe3＋ ion.
基金Project supported by the University of Copenhagen,the Novo Nordisk Foundation(grant number 4096)Carlsbergfondet,the Villum Foundation(grant number 14922)ENS Lyon。
文摘Sensing of analyte s in biological fluids and biotechnological production media remains a challenge.He re,the luminescent response of the europium(Ⅲ)complex of 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid(DO3A)to bicarbonate was investigated in detail.The response of Eu.DO3A to changes in bicarbonate concentration was studied in different buffers,and the influence of ionic strength,pH,and specific ions was determined.The response is found to depend on pH and ionic strength,but it is not possible to separate contributions from the sensing event from those in the bicarbonate activity.Prior to demonstrating the ability to determine the bicarbonate concentration in bioproduction media and serum,the influence of competing carboxy anions was evaluated.It is established that while competing anions bind stronger to the responsive complex,at the relevant concentration their contribution to the recorded signal is negligible.We are thus able to conclude that Eu.DO3A is a good platform for building a bicarbonate sensor.
基金supported by Key Projects of Natural Science Research in Universities of Anhui Province(No.KJ2018A0409)National Undergraduate Training Programs for Innovation and Entrepreneurship(No.201810375012,201810375039)
文摘A new complex, {[Cd（BIDPT）（NBA）]}n（1）, was synthesized from the selfassembly of BIDPT（BIDPT = 4,4?-bis（imidazol-l-yl）diphenyl thioether） and H2NBA（H2 NBA = 4,4?-azanediyldibenzoic acid） ligands with Cd（Ⅱ）. 1 was characterized by infrared spectroscopy, powder X-ray diffraction, elemental analysis, and thermogravimetry measurement. 1 crystallizes in monoclinic system, space group P21/c with a = 8.8204（1）, b = 29.835（3）, c = 10.3813（1） ?, β = 96.180（2）°, V = 2730.7（5） ?3, Z = 4, C32H22CdN5O4S, Mr = 685.01, Dc = 1.666 g/cm3, μ = 0.926 mm-1, R = 0.0548 and wR = 0.1528. 1 features a parallel structure with 3-connected hcb network and the adjacent 2 D networks are stacked together via C–H···π interaction to form a 3 D network. Its application in detecting metal cations and inorganic anions was explored. 1 exhibits excellent photoluminescence sensing for Fe3+ and Cr2O72- ions. And the mechanism of quenching is also studied.
基金financially supported by the National Natural Science Foundation of China(Grant No.51108122 and 21404035)University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province(UNPYSCT-2016075)Key laboratory of Functional Inorganic material Chemistry(Heilongjiang University),Ministry of Education.
文摘A novel coordination polymer Zn(DMA)(TBA)(1)(H_(2)TBA=4-(1H-tetrazol-5-yl)-benzoic acid)features a unique two-dimensional(2D)network structure,exhibiting excellent luminescence and good stability in both water and other organic solvents.1 shows excellent selectivity.
基金supported by the National Natural Science Foundation of China(21571142)and Developing Science Funds of Tongji University.
文摘N-Methylformamide(NMF)has been recognized as one of the most important industrially relevant solvents and a crucial intermediate used in industrial processes.However,indiscriminate use of NMF has been perceived as a threat to sustainable development owing to the lack of effective monitoring.In this study,a bimetallic lanthanide metal–organic framework(LMOF)with a fast response time and high sensitivity for monitoring of NMF is designed and fabricated,which also exhibits strong fluorescence.The response emission signals toward NMF range from red to green and are significantly correlated with the increase in the solvent concentration of NMF.Considering the fast response and excellent sensitivity results,a logic gate with AND functions for NMF is constructed.
基金upported by the National Natural Science Foundation of China(Grant No.21871122 and 21901095)the Gansu Planning Projects on Science and Technology(21JR7RA512)the Fundamental Research Funds for the Central Universities(Grant No.lzujbky-2021-8,lzujbky-2021-kb06,lzujbky-2021-kb17).
文摘In order to reduce usage cost and simplify the detection process,it is necessary to develop multifunc-tional and multi-emitter Ln-MOF luminescent sensors.The structure and property of Ln-MOFs are mainly controlled by ligands.As a typical aromatic nucleus,naphthalene groups not only can emit fluorescence and regulate the energy levels of a ligand but also can participate inπ-πstacking.As a type of directional weak interaction,hydrogen bonding interactions have caught wide attention in catalysis,molecular reco-gnition,self-assembly,etc.So we designed a“V”shaped ligand containing naphthalene groups and“O■C-NH”groups as guided by DFT calculations.The obtained Eu-MOF can achieve simultaneous luminescence of the ligand and Eu^(3+).Single crystal X-ray diffraction revealed thatπ-πstacking inter-actions and hydrogen bonding interactions played an important role in the crystallization process.The luminescence spectra showed that the Eu-MOF has two luminescent centers and can be developed as a ratiometric luminescent sensor.The luminescence of the Eu-MOF can undergo an obvious color change from red to white as the temperature rises from 120 to 400 K and the Eu-MOF has a satisfactory relative sensitivity and a small temperature uncertainty.Moreover,the Eu-MOF can detect picric acid selectively and the K_(SV) can reach 53339 M^(−1).Thus,the Eu-MOF can be used as a multifunctional and multi-emitter luminescent sensor and the designed strategy also can provide inspiration for further research on Eu-MOFs.
基金supported by the Joint Fund Project of the Natural Science Foundation of Jilin Province(YDZJ202101ZYTS052)the Open Project Program of Key Laboratory of Preparation and Application of Environmental Friendly Materials(Jilin Normal University)+1 种基金Ministry of Education,China(No.2021008)the Foundation of Changchun University of Science and Technology(XQNJJ-2019-12 and XJJLG-2019-03).
文摘Five isostructural lanthanide metal–organic frameworks [Ln(BDPO)(H_(2)O)_(4)] (Ln = Eu for CUST-623, Tb for CUST-624, Gd for CUST-625, Dy for CUST-626, and Sm for CUST-627, BDPO = N,N'-bis(3,5-dicarboxyphenyl)-oxalamide) were synthesized by the solvothermal method. Single-crystal X-ray diffraction shows that Ln-MOFs manifest framework structures with two kinds of 1D open channels in the b-axis direction. Dual emission luminescent thermometer films were successfully prepared by immobilizing Eu_(x)Tb_(0.02−x)-BDPO into polyvinyl alcohol (PVA) aqueous solution, which features the integrity of MOF powders, proving their excellent processability. Moreover, Eu0.002Tb0.018-BDPO@PVA shows excellent temperature sensing performance with a high sensitivity of 3.7% K^(−1) in the temperature range of 303 K–423 K. CUST-623 and CUST-624 can be used as multiresponse fluorescent sensors for detecting Fe^(3+), Cr_(2)O_(7)^(2−), CrO_(4)^(2−) and TNP. In addition, the mechanism of fluorescence sensing is investigated by infrared (IR) spectroscopy, powder X-ray diffraction (PXRD) and ultraviolet–visible (UV-vis) spectroscopy. This work provides a general method for constructing Ln-MOF sensor materials with multifunctional luminescence characteristics.
基金financially supported by the National Natural Science Foundation of China(No.21771096)。
文摘The fast,sensitive and selective detection of some antibiotics and heavy metal cations in water is highly desirable for environmental protection and human health,but it is still currently challenging.In this work,a new luminescent Eu(Ⅲ)-based metalorganic framework(MOF),{[(CH_(3))_(2)NH_(2)][Eu(L)2(H_(2)O)_(2)]·xDMF}n(1)[H_(2)L=4,4’-((naphthalene-1,4-dicarbonyl)bis(azanediyl))dibenzoic acid],was solvothermally synthesized.Complex 1 exhibits good water stability and luminescent property and could serve as a bifunctional ratiometric luminescent sensor for fast,sensitive and selective detection of ornidazole(ODZ)and Hg^(2+)in aqueous solution.The corresponding luminescent mechanism has also been discussed.This work indicates that 1 as a promising luminescent material exhibits luminescent quenching behavior for ODZ and luminescent enhancement behavior for Hg^(2+)in H_(2)O,which will promote the practical application of Ln-MOF-based ratiometric luminescent sensors in monitoring antibiotics and metal ions pollutants in the environmental water matrices.
基金Project supported by the Ministry of Science and Technology of China (Nos. G2000078104 G2000077502) and the National Natural Science Foun-dation of China and Bureau for the Basic Research of Chinese Academy of Sciences.
文摘The platinum(II) terpyridyl acetylide complex [Pt(terpy)(C≡CR)]ClO4 (terpy=2,2'∶6'2''-terpyridine, R=CH2CH2CH3) (1) was incorporated into Nafion membranes. At high loading the dry membranes exhibit intense photoluminescence with max at 707 nm from the 3MMLCT state, which was not observed in fluid solution. Upon exposure to the vapor of polar volatile organic compounds (VOC), this photoluminescence was significantly red-shifed. This process was fully reversible when the VOC-incorporated membrane was dried in air. The dramatic and reversible changes in the emission spectra made the Nafion-supported complex as an interesting sensor candi-date for polar VOC.
基金supports of the National Natural Science Foundation of China(Nos.21201037,21405019 and 21171022)the Natural Science Foundation of Anhui Province(No. 1408085QB39)+2 种基金the Innovation Training Program for the Anhui College students(Nos.AH201310371039 and AH201310371041)Anhui Provincial Key Laboratory for Degradation and Monitoring of the Pollution of the Environment,and the Natural Science Foundation of Sichuan Provincial Department of Education(No. 13ZB0056)Analytical and Measurements Fund of Beijing Normal University
文摘A dual colorimetric and luminescent sensor based on a heteroleptic ruthenium dye [Ru（Hipdpa）（Hdcb- py）（NCS）2]^-.0.5H^＋ 0.5[N（C4H9）4]＋ Ru（Hipdpa） {where Hdcbpy = monodeprotonted-4,4＇-dicarboxy-2,2＇- bipyridine and Hipdpa = 4-（1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl）-N,N-diphenylaniline} for selective detection of Hg2. is presented. The results of spectrophotometric titrations revealed an evident luminescence intensity enhancement （I/Io = 11 ） and a considerable blue shift in visible absorption and luminescence maxima with the addition of rig2.. The sensitive response of the optical sensor on Hg^2＋ was attributed to the binding of the electron-deficient Hg^2＋ to the electron-rich sulfur atom of the thiocyanate （NCS） ligand in the Ru（Hipdpa）, which led to an increase in the energy gap between the highest occupied molecular orbital （HOMO） and the lowest unoccupied molecular orbital （LUMO）. Accordingly, the blue shift in the absorption spectrum of Ru（Hipdpa） due to the binding of Hg2. was obtained. Ru（Hipdpa） was found to have decreased Hg2~ detection limit and improved linear region as compared to di（tetrabutylammonium） cis-bis（isothiocyanato）bis（2,2＇-bipyridine-4-carboxylic acid-4＇- carboxylate）ruthenium（ll） N719. Moreover, a dramatic color change from pink to yellow was observed, which allowed simple monitoring of Hg^2＋ by either naked eyes or a simple colorimetric reader. Therefore, the proposed sensor can provide potential applications for Hg2＊ detection.
基金supported by the“Pioneer”and“Leading Goose”R&D Program of Zhejiang(Grant No.2024C01192)National Natural Science Foundation of China(Grant Nos.62425502,62375060,62205081,62405073,and 52272013)+1 种基金Zhejiang Provincial Natural Science Foundation(Grant No.LMS25F050001)Shanghai Pilot Program for Basic Research(Grant No.22JC1403200)。
文摘Detecting hazardous hydrogen halides(HX,X=Cl,Br,and I)gas is critical for human health and ecological safety.A luminescent sensor based on anion exchange reaction(AER)in perovskite could offer a cost-effective approach.However,resolving the challenging issues of instability and the acceleration requirement of AER is highly desired for practical applications.Here,we develop an ultra-rapid,sensitive,and reusable HCl luminescent gas sensor through nanoconfining MAPbBr3 quantum dots(QDs)into a transparent nanoporous glass(NG)matrix,successfully extending perovskite glass to the organic-inorganic system,which exhibits enhanced AER sensitivity.Utilizing enhanced transport efficiency of reactants within NG,HCl gas could be rapidly adsorbed into the nanopores and undergo ultra-rapid AER with the embedded perovskite QDs.In addition,the device stability could be fostered by the physical protection of glass matrix.After being simply integrated with UV LED,the MAPbBr3-NG exhibits an ultra-rapid response time within 2 s at a HCl gas concentration of 5 ppm.Furthermore,this luminescent gas sensor demonstrates robust performance,retaining functionality over 10 reuse cycles.This compact,cost-effective,and highly sensitive device with rapid response capability could open a promising avenue for research on HX detection while expanding the practical applications of perovskite-based devices.
基金support from the National Natural Science Foundation of China(22475012,22101017)Y.F.S.acknowledges support from the National Natural Science Foundation of China(22288102,22178019,22208013,22378012)+2 种基金the Fundamental Research Funds for the Central Universities(XK1802-6,XK1803-05,XK1902)Q.Q.acknowledges support from the National Natural Science Foundation of China(22278394)the Dalian Institute of Chemical Physics(DICPI202227).
文摘Chiral recognition,particularly the recognition of different enantiomers of chiral drugs,is important for human life and health safety.Here,we designed a two-dimensional(2D)confined polyoxometalate-based chiral luminescence sensor by encapsulating luminescent[EuW_(10)O_(36)]^(9-)clusters(EuW_(10))within the chiral 2D interlayer of layered double hydroxides modified with chiral ionic liquids(L-CIL-Mg_(3)Al-EuW_(10)).
基金supported by the National Natural Science Foundation of China(Nos.21771095 and 22061019)the Natural Science Foundation of Shandong Province(Nos.ZR2021MB114 and ZR2021MB073)the Youth Innovation Team of Shandong Colleges and Universities(No.2019KJC027).
文摘The abuse of antibiotics has brought great harm to the human living environment and health,so it is extremely significant to develop an efficient and simple method to detect trace antibiotic residues in various wastewaters.Herein,a new two-dimensional(2D)Cd-based metal−organic framework(Cd-MOF,namely LCU-111)and its mixed matrix membranes(MMMs)is sifted as luminescence sensors for efficient monitoring antibiotic nitrofurazone(NFZ)in various aqueous systems and applied as visible fingerprint identifying.The LCU-111 has good selectivity,sensibility,reproducibility and anti-interference for luminescent quenching NFZ with low detection limits(LODs)of 0.4567,0.3649 and 0.8071 ppm in aqueous solution,HEPES biological buffer,and real urban Tuhai River water,respectively.Interestingly,the luminescent test papers and MMMs allow the NFZ sensing easier and more rapid by naked eyes,only with a low LOD of 0.8117 ppm for MMMs sensor.Notably,by combining multiple experiments with density functional theory(DFT)calculations,the photo-induced electron transfer(PET)quenching mechanism is further elucidated.More importantly,potential practical applications of LCU-111 for latent fingerprint visualization provide lifelike evidences for effective identification of individuals,which can be applied in criminal investigation.
基金financially supported by the National Natural Science Foundation of China(21801107)the Natural Science Foundation of Shandong Province(ZR2018BB005)the Youth Innovation Team of Shandong Colleges and Universities(2019KJC027)。
文摘Various ions and antibiotics,widely used in industry and clinical medicine,respectively,are massively discharged to atmosphere and water,resulting in severe pollutions on environment and potential threats to human health.Besides,amino acids,the primary substances for the establishment of proteins,cells and tissues,are crucial to human health.Therefore,seeking effective and practicable materials to detect aforesaid analytes is vitally meaningful.Metal-organic frameworks centered with lanthanide ions(Ln-MOFs),also known as lanthanide coordination polymers,are considered as a charming category of multi-functional hybrid crystalline materials with fascinating structures and incomparable luminescent characteristics.Benefited from their unique merits,Ln-MOFs have been largely developed as excellent luminescent sensors for fast and efficient sensing various analytes.In this review,we aim to introduce some of the recent researches between 2018 to 2022 on Ln-MOFs applied as chemical sensors for ions,antibiotics and amino acids based on luminescent quenching and enhancing effects,and provide an update and summary for the latest progresses in this field.
基金supported by the National Program for Support of Top-Notch Young Professionalsthe Synergetic Innovation Center for Organic Electronics and Information Displaysthe Priority Academic Program Development of Jiangsu Higher Education Institutions(YX03001).
文摘Gold nanoclusters(Au NCs)are promising luminescent nanomaterials due to their outstanding optical properties.However,their relatively low quantum yields and environment-dependent photoluminescence properties have limited their biological applications.To address these problems,we developed a novel strategy to prepare chitosan oligosaccharide lactate(Chi)-functionalized Au NCs(Au NCs@Chi),which exhibited emission with enhanced quantum yield and elongated emission lifetime as compared to the Au NCs,as well as exhibited environment-independent photoluminescence properties.In addition,utilizing the free amino groups of Chi onto Au NCs@Chi,we designed a FRET-based sensing platform for the detection of hydrogen sulfide(H_(2)S).The Au NCs and the specific H_(2)S-sensitive merocyanine compound were respectively employed as an energy donor and acceptor in the platform.The addition of H_(2)S induced changes in the emission profile and luminescence lifetime of the platform with high sensitivity and selectivity.Utilization of the platform was demonstrated to detect exogenous and endogenous H_(2)S in vitro and in vivo through wavelength-ratiometric and time-resolved luminescence imaging(TLI).Compared to previously reported luminescent molecules,the platform was less affected by experimental conditions and showed minimized autofluorescence interference and improved accuracy of detection.
基金supported by National Science Fund for Distinguished Young Scholars(21625601)Major Project of National Natural Science Foundation of China(91334203)Outstanding Talent Fund from Beijing University of Chemical Technology
文摘Two porous organic polymer nanotubes(PNT-2 and PNT-3) were synthesized via Ni-catalyzed Yamamoto reaction, using2,4,6-tris-(4-bromo-phenyl)-[1,3,5]-triazine(TBT) as one monomer, and 2,7-dibromopyrene(DBP) or 1,3,6,8-tetrabromopyrene(TBP) as another monomer. The scanning electron microscope(SEM) images show that both PNT-2 and PNT-3 possess clear hollow tube structures. Luminescent measurements indicate that both PNT-2 and PNT-3 can serve as luminescent probe for highly selective and sensitive detection of Fe^(3+) by luminescent quenching effect. Absorption competition quenching(ACQ) mechanism is also proposed to explain luminescent quenching behavior, i.e., the overlap of the UV-spectra between Fe^(3+) and PNTs causes the energy competition, and therefore leads to luminescent quenching. Moreover, both PNT-2 and PNT-3 still show high selectivity and sensitivity for sensing Fe^(3+) in 10% ethanol aqueous solution, which means that the two porous PNTs are promising candidates as luminescent probes for detecting Fe^(3+) in practical applications.
基金supported by the Robert A.Welch Foundation through an endowed chair(grant no.A-0030)to H.-C.Z.the National Natural Science Foundation of China(grant nos.22471130,22261132509,22435002,and 22121005).
文摘Perfluorooctanoic acid(PFOA),a persistent environmental pollutant,poses serious health risks and remains challenging to detect due to its low light absorption and weak binding affinity.Luminescence sensing offers a powerful approach to its rapid and quantitative detection,with electron transfer playing a critical role when energy transfer is limited by the analyte’s unfavorable energy-level alignment.Lanthanidebased metal–organic frameworks(MOFs),featuring sharp emissions,long-lived excited states,and tunable electronic structures,are particularly promising for such applications owing to their ability to precisely regulate electron transfer pathways through structural modulation.However,the impact of the coordination mode and symmetry on sensing performance remains poorly understood due to its complex mechanisms.Herein,we report a series of eight europiumbased MOFs,Eu_(2)(FDA)_(3)(solvent)x,synthesized using a single ligand to enable systematic investigation of the relationship between Eu^(3+) coordination symmetry and PFOA sensing behavior.Notably,MOFs with lower coordination symmetry exhibit significantly higher quenching efficiency due to increased energy-level splitting that promotes electron transfer.This study establishes a clear structurefunction correlation and provides valuable insights for the rational design of MOF-based sensors targeting spectroscopically challenging contaminants,thereby deepening the understanding of luminescence sensing mechanisms based on structure-driven signal transduction processes.
基金supported by the Robert A.Welch Foundation through an endowed chair(A-0030)National Natural Science Foundation of China(grant nos.22471130 and 22261132509)We also thank the Fonds de la Recherche Scientifique-FNRS(PDR T.0095.21,FC 53249).
文摘Open metal sites(OMSs)represent a distinctive feature of metal-organic frameworks(MOFs),intertwined with vip accommodation and energy transfer within nanosized pores.Fine-tuning OMSs provide an effective approach to regulating MOF’s responsiveness and binding affinity towards vips,allowing for the construction of luminescent sensors for specific analytes.Such a strategy remains unexplored due to the inherent complexity of the systems and sensing mechanisms.Herein,we delicately regulated the OMSs in PCN-700 through multiple synthetic methodologies,including direct synthesis,linker installation,and linker exchange.The resultant MOFs consist of Zr6-clusters featuring various coordination numbers.Notably,PCN-700-8u with unsaturated 8-coordinated Zr-clusters exhibited the highest sensitivity in detecting a toxic pesticide pentachloronitrobenzene(PCNB)due to the presence of strong coordination interaction,as validated through single crystal X-ray diffraction directly.PCN-700-10u/12u bearing unsaturated 10/12-coordinated clusters perform lower quenching efficiencies than PCN-700-8u,but higher than PCN-700-12s with saturated clusters.In contrast,all these MOFs exhibit similar quenching efficiencies towards hexachlorobenzene for the absence of coordination interaction.This study not only develops a cost-effective and easily attainable material for PCNB detection,but also illuminates the pivotal importance of OMSs in customizing MOF-based sensors for practical applications.
基金Supported by the Natural Science Foundation of Fujian Province (2017J01746)National Natural Science Foundation of China (51972061)。
文摘The aluminum based MOFs compound, MIL-96(Al), has been studied as a luminescence sensor by incorporating of Eu3+ ions, which renders the compound strong red-light emission. The as-synthesized MIL-96(Al):Eu3+ nanocrystals exhibit water dispersibility and environmental stability, which are general requirement for an ideal sensing material. The MIL-96(Al):Eu3+ nanocrystals show excellent selective detection ability on Fe3+ ions in aqueous solution with value of low detection limit 20 μM. Meanwhile, it also exhibits excellent selective detection ability on CrO42- and Cr2O72- in aqueous solution with value of low detection limit 10 and 22 μM, respectively. The results of this study show that MIL-96(Al):Eu3+ nanocrystals could be used as a multi-responsive luminescent senor for Fe3+ and Cr(Ⅵ) species in aqueous solution. The possible luminescence quenching mechanism has also been discussed.
