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1.
Chemistry ; : e202402439, 2024 Sep 15.
Artículo en Inglés | MEDLINE | ID: mdl-39278828

RESUMEN

A well-judged combination of a high axial ligand field and a bridging radical ligand in a dinuclear lanthanide complex provides a single-molecule magnet with a higher effective energy barrier for magnetic relaxation and blocking temperature compared to its non-radical analog due to significant magnetic exchange coupling between radical and Ln(III) ions. In this work, we report two chloranilate (CA) bridged dinuclear dysprosium complexes, [{(bbpen)Dy(µ2-CA)Dy(bbpen)}] (1Dy) and [{(bbpen)Dy(µ2-CA•)Dy(bbpen)}-{CoCp2}+] (2Dy), where 2Dy is the radical bridged Dy-complex obtained via the chemical reduction of bridging CA moiety (H2bbpen = N,N'-bis(2-hydroxybenzyl)-N,N'-bis(2-methylpyridyl)ethylenediamine). The presence of high electronegative phenoxide moiety enhances the axial anisotropy of pseudo-square antiprismatic Dy(III) ions. The diffused spin of radical is efficiently coupled with anisotropic Dy(III) centres and decreases the quantum tunnelling of magnetization (QTM) in the magnetic relaxation process. The magnetic relaxation of 1Dy follows Orbach, Raman, and QTM processes whereas for 2Dy it follows Orbach and Raman Processes. Due to less involvement of the QTM relaxation process, 2Dy shows a higher thermal energy barrier (Ueff = 700 K) and a high blocking temperature (6.7 K), compared to its non-radical analog. Remarkably, the radical coupled 2Dy complex shows the highest energy barrier among the radical bridged Dy(III)-based SMMs to date.

2.
Spectrochim Acta A Mol Biomol Spectrosc ; 325: 125046, 2024 Aug 30.
Artículo en Inglés | MEDLINE | ID: mdl-39217951

RESUMEN

A blue-emitting phosphor designed by lanthanum (III) coordinated with two 1,10-Phenanthroline and three nitrate ligands, [La(Phen)2(NO3)3], was obtained by an effective and simple precipitation method. Fourier transform infrared spectroscopy (FTIR) and powder X-ray diffraction (PXRD) revealed the coordination modes in the compound and the chemical structure, crystallizing in a monoclinic system in the C2/c space group. The luminescence properties, absolute quantum yield (ϕ), and luminescence lifetime decay (τ) were determined by photoluminescence spectroscopy. Under a 350 nm excitation, the sample presents three emission bands corresponding to the π* → π transitions belonging to the organic ligand. The luminescence lifetime (τ) was determined through a monoexponentially fit, obtaining a value of 5616 ns. The [La(Phen)2(NO3)3] complex exhibits an absolute quantum yield of 3 % with the same excitation conditions. In addition, the photometric analysis shows that the luminescent response to a 350 nm excitation is that of a blue-emitting high-purity phosphor with 96 % and chromatic coordinates of 0.15, 0.05. The temperature-dependent luminescence properties revealed considerable thermal stability in the 20-150 °C range with a signal loss of 47 % and an activation energy of thermal quenching (ΔE) of 0.13 eV, the first value reported for a lanthanum complex based on 1,10-Phenanthroline.

3.
Molecules ; 29(15)2024 Aug 04.
Artículo en Inglés | MEDLINE | ID: mdl-39125096

RESUMEN

This review focuses on optical properties of compounds in which at least one phosphonate group is directly attached to a heteroaromatic ring. Additionally, the synthesis and other applications of these compounds are addressed in this work. The influence of the phosphonate substituent on the properties of the described compounds is discussed and compared with other non-phosphorus substituents, with particular attention given to photophysical properties, such as UV-Vis absorption and emission, fluorescence quantum yield and fluorescence lifetime. Considering the presence of heteroatom, the collected material was divided into two parts, and a review of the literature of the last thirty years on heteroaryl phosphonates containing sulfur and nitrogen atoms in the aromatic ring was conducted.

4.
Angew Chem Int Ed Engl ; : e202413069, 2024 Jul 24.
Artículo en Inglés | MEDLINE | ID: mdl-39045802

RESUMEN

Lanthanide-based upconversion molecular complexes have potential application in diverse fields and attracted considerable research interest in recent years. However, the similar coordination reactivity of lanthanide ions has constrained the designability of target molecule with well-defined structure, and many attempts obtained statistical mixtures. Herein, an ion-paired Yb-Eu heteronuclear complex [Eu(TpPy)2][Yb(ND)4] (TpPy = tris[3-(2-pyridyl)pyrazolyl]hydroborate, ND = 3-cyano-2-methyl-1,5-naphthyridin-4-olate) was designed and synthesized. Thanks to the radius difference between Eu3+ (1.07 Å) and Yb3+ (0.98 Å) ions, the hexadentate TpPy ligand was selected to coordinate with Eu3+ and the Yb3+ with a smaller radius was chelated by bidentate ND ligand. As a result, the sites of Eu3+ and Yb3+ in the complex can be clarified by high-resolution mass spectrometry and single-crystal structure analysis. Upon the excitation of Yb3+ at 980 nm, the upconversion emission of Eu3+ was realized through a cooperative sensitization process. Furthermore, [Eu(TpPy)2][Yb(ND)4] demonstrated excellent photostability during continuous high-power density 980 nm laser irradiation, with a LT95 (the time to 95% of the initial emission intensity) of 420 minutes. This work provides the first example of a pure ion-paired Yb-Eu heteronuclear complex upconversion system and may bring insights into rational design of lanthanide-based upconversion molecular complexes.

5.
J Fluoresc ; 2024 May 17.
Artículo en Inglés | MEDLINE | ID: mdl-38758342

RESUMEN

Dipicolinic acid (DPA) is a prominent biomarker for Anthrax disease. Bacillus anthracis bacterial endospores is composed of DPA as the significant component, which on over inhalation can cause severe health issues. Such contagious and life-threatening pathogens can be employed as bioweapons or biothreat agents for spreading bioterrorism which is a major risk for national security and public health concerns. Hence, effective detection or a surveillance system is essential for preventing the growth of bioterrorism events. Herein, we have developed a Terbium - 1,10 Phenanthroline (Tb-Phen) based lanthanide luminescence complex with bright green fluorescence. On addition of DPA, the green fluorescence is turn-off at a linear range from 0.6 to 4.762 mM. In this effect, 5D4- 7F5 transition caused by 1,10-phenanthroline to Tb3+ at 544 nm is restricted due to energy transfer quenching and Inner Filter Effect (IFE). The developed probe shows good sensitivity towards the detection of DPA with other coexisting biomolecules and ions with a low Limit of Detection (LOD) of 5.029 µM. The practical feasibility was evaluated in paper strip assay and extended in real samples such as human serum and tap water with satisfactory recovery percentage. Thereby, probe finds promising application in sensing of anthrax spore biomarker (DPA) and biothreat agents.

6.
Chemistry ; 30(35): e202400911, 2024 Jun 20.
Artículo en Inglés | MEDLINE | ID: mdl-38651349

RESUMEN

In this work, we developed two kinds of co-crystal assemblies systems, consisting of discrete mononuclear Yb3+ and Er3+ and mononuclear Yb3+ and Pr3+, which can achieve Er3+ and Pr3+ upconversion luminescence, respectively, by Yb3+ sensitization under 980 nm excitation. The structure and composition of two co-crystal assemblies were determined by single crystal X-ray diffraction. By investigation of the series of two assemblies, respectively, it is found that the strongest upconversion luminescence is both obtained when the molar ratio of Yb3+ and Ln3+ (Ln=Er or Pr) is 1 : 1. The energy transfer mechanism of Er3+ assemblies is determined as energy transfer upconversion, while that of Pr3+ assemblies is determined as energy transfer upconversion and cooperative sensitization upconversion. This is the first example of Pr3+ upconversion luminescence at the molecular dimension at room temperature, which enriches the research in the field of upconversion luminescence with lanthanide complexes.

7.
Talanta ; 274: 126000, 2024 Jul 01.
Artículo en Inglés | MEDLINE | ID: mdl-38608630

RESUMEN

Luminescent ß-diketonate-europium(III) complexes have been found a wide range of applications in time-gated luminescence (TGL) bioassays, but their poor water solubility is a main problem that limits their effective uses. In this work we propose a simple and general strategy to enhance the water solubility of luminescent ß-diketonate-europium(III) complexes that permits facile synthesis and purification. By introducing the fluorinated carboxylic acid group into the structures of ß-diketone ligands, two highly water-soluble and luminescent Eu3+ complexes, PBBHD-Eu3+ and CPBBHD-Eu3+, were designed and synthesized. An excellent solubility exceeding 20 mg/mL for PBBHD-Eu3+ was found in a pure aqueous buffer, while it also displayed strong and long-lived luminescence (quantum yield φ = 26%, lifetime τ = 0.49 ms). After the carboxyl groups of PBBHD-Eu3+ were activated, the PBBHD-Eu3+-labeled streptavidin-bovine serum albumin (SA-BSA) conjugate was prepared, and successfully used for the immunoassay of human α-fetoprotein (AFP) and the imaging of an environmental pathogen Giardia lamblia under TGL mode, which demonstrated the practicability of PBBHD-Eu3+ for highly sensitive TGL bioassays. The carboxyl groups of PBBHD can also be easily derivatized with other reactive chemical groups, which enables PBBHD-Eu3+ to meet diverse requirements of biolabeling technique, to provide new opportunities for developing functional europium(III) complex biolabels serving for TGL bioassays.


Asunto(s)
Europio , Solubilidad , Agua , Europio/química , Agua/química , Humanos , Mediciones Luminiscentes/métodos , Albúmina Sérica Bovina/química , Complejos de Coordinación/química , Complejos de Coordinación/síntesis química , Giardia lamblia/efectos de los fármacos , Luminiscencia , Animales , Bioensayo/métodos , Sustancias Luminiscentes/química , Sustancias Luminiscentes/síntesis química , Estreptavidina/química , Factores de Tiempo , Bovinos , Cetoácidos/química
8.
Anal Chim Acta ; 1287: 342063, 2024 Jan 25.
Artículo en Inglés | MEDLINE | ID: mdl-38182371

RESUMEN

BACKGROUD: Single oxygen (1O2), the molecular oxygen at its excited state, plays a crucial role in the photodynamic therapy (PDT) of some diseases owing to its strong oxidizing property to destroy malignant cells. Although the fluorescent probe technique has proven its powerful application abilities for detection of 1O2 in biological systems, most of the reported fluorescent probes suffered from the interference of background autofluorescence of biological samples. It is clear that the real-time and in situ, background-free fluorescent detection of 1O2 generated in live cells, especially in some organelles, is of great significance for understanding the action mechanism of PDT drugs. RESULTS: By introducing a lysosome-anchoring motif, a morpholine moiety, into a 1O2-specifically-reactive terpyridine polyacid ligand, [4'-(9-anthryl)-2,2':6',2″-terpyridine-6,6″-diyl] bis(methylenenitrilo) tetrakis (acetic acid) (ATTA), and chelating with lanthanide ions (Eu3+ or Tb3+), two lanthanide complex-based "turn-on" luminescent probes that can be used for the background-free time-gated luminescent (TGL) detection of lysosomal 1O2, Lyso-ATTA-Eu3+ and Lyso-ATTA-Tb3+, have been developed. The probes exhibit fast luminescence responses (within 2.5 min) towards 1O2 with high selectivity and sensitivity (<0.75 µM) in a wide pH range (4-11). And the excellent lysosome-localization performance of the probes allowed them to be used for the monitoring of endogenous 1O2 in lysosomes, which enabled the variability of lysosomal-1O2 concentrations induced by different photosensitizers to be successfully discriminated. Furthermore, by doping Lyso-ATTA-Eu3+ into the polyethylene glycol (PEG) hydrogel, the smart luminescent sensor film, PEG-Lyso-ATTA-Eu3+, was prepared, and successfully used for the detection of the on-site 1O2 production during the PDT process of psoriatic disease in model mice. SIGNIFICANT: Two lysosome-targetable background-free TGL probes for 1O2 were firstly reported. The developed smart luminescent sensor film could be a powerful tool for the clinical monitoring of PDT on skin diseases without using sophisticated and expensive instruments.


Asunto(s)
Elementos de la Serie de los Lantanoides , Oxígeno Singlete , Animales , Ratones , Luminiscencia , Oxígeno , Lisosomas , Materiales Biocompatibles , Colorantes Fluorescentes
9.
Biomater Res ; 27(1): 119, 2023 Nov 22.
Artículo en Inglés | MEDLINE | ID: mdl-37990349

RESUMEN

BACKGROUND: Non-intrusive imaging of gastrointestinal (GI) tract using computed tomography (CT) contrast agents is of the most significant issues in the diagnosis and treatment of GI diseases. Moreover, spectral CT, which can generate monochromatic images to display the X-ray attenuation characteristics of contrast agents, provides a better imaging sensitivity for diagnose inflammatory bowel disease (IBD) than convention CT imaging. METHODS: Herein, a convenient and one-pot synthesis method is provided for the fabrication of small-molecule lanthanide complex Holmium-tetraazacyclododecane-1, 4, 7, 10-tetraacetic acid (Ho-DOTA) as a biosafe and high-performance spectral CT contrast agent for GI imaging with IBD. In vivo CT imaging was administered with both healthy mice and colitis mice induced by dextran sodium sulfate. RESULTS: We found that Ho-DOTA accumulated in inflammation sites of large intestines and produced high CT contrast compared with healthy mice. Both in vitro and in vivo experimental results also showed that Ho-DOTA provided much more diagnostic sensitivity and accuracy due to the excellent X-ray attenuation characteristics of Ho-DOTA compared with clinical iodinate agent. Furthermore, the proposed contrast media could be timely excreted from the body via the urinary and digestive system, keeping away from the potential side effects due to long-term retention in vivo. CONCLUSION: Accordingly, Ho-DOTA with excellent biocompatibility can be useful as a potential high-performance spectral CT contrast agent for further clinical imaging of gastrointestinal tract and diagnosis of intestinal system diseases.

10.
Angew Chem Int Ed Engl ; 62(44): e202312308, 2023 Oct 26.
Artículo en Inglés | MEDLINE | ID: mdl-37698110

RESUMEN

Metal-based upconversion luminescence transforming high-energy photons into low-energy photons is an attractive anti-Stokes shift process for fundamental research and promising applications. In this work, we developed the upconversion luminescence in co-crystal assemblies consisting of discrete mononuclear Yb and Sm complexes. The characteristic visible emissions of Sm3+ were observed under the excitation of absorption band of Yb3+ at 980 nm. A series of co-crystal assemblies were investigated based on mononuclear Yb and Sm complexes, and the strongest luminescence was obtained when the molar concentration between Yb3+ and Sm3+ is equivalent. The crystal structure was fully characterized by the single crystal X-ray diffraction and upconverting energy transfer mechanisms were verified as cooperative sensitization upconversion and energy transfer upconversion. This is the first example of Sm3+ -based upconverting luminescence in discrete lanthanide complexes which present as co-crystal assemblies at room temperature.

11.
Front Chem ; 11: 1244266, 2023.
Artículo en Inglés | MEDLINE | ID: mdl-37614706

RESUMEN

The investigation involved examining the binding of two lanthanide complexes, specifically those containing Holmium (Ho) and Dysprosium (Dy), with a ligand called 1, 10-phenanthroline (phen), and bovine serum albumin (BSA). The evaluation was carried out utilizing fluorescence measurements, Förster theory, and docking studies. The findings indicated that both the Ho-complex and Dy-complex possessed a significant ability to quench the emission of the protein. Furthermore, the primary mechanism of interaction was identified as a static process. The Kb values indicate a strong tendency of these complexes for binding with BSA. The Kb values show the strangely high affinity of BSA to complexes and the following order for binding affinity: Ho-complex > Dy-complex. The thermodynamic parameters were found to be negative, affirming that the main forces driving the interaction between BSA and the lanthanide complexes are van der Waals engagement and hydrogen bonds. Additionally, the investigation included the examination of competition site markers, and molecular docking proposed that the engagement sites of the Ho-complex and Dy-complex with BSA were predominantly located in site 3 (specifically, subdomain IB). Moreover, the Ho-complex and Dy-complex were specifically chosen for their potential anticancer and antimicrobial properties. Consequently, these complexes could present promising prospects as novel candidates for anti-tumor and antibacterial applications.

12.
Front Chem ; 11: 1154012, 2023.
Artículo en Inglés | MEDLINE | ID: mdl-37123879

RESUMEN

A novel design strategy of stacked organic fluorophores using dinuclear lanthanide (Ln(III)) complexes is demonstrated for the formation of excimer. The dinuclear Ln(III) complexes are composed of two Ln(III) (Eu(III) or Gd(III)) ions, six hexafluoroacetylacetonate (hfa), and two pyrene-based phosphine oxide ligands. Single-crystal analysis revealed a rigid pyrene-stacked structure via CH-F (pyrene/hfa) intramolecular interactions. The rigid aggregation structures of the two-typed organic ligands around Ln(III) resulted in high thermal stability (decomposition temperature: 340°C). The aggregated ligands exhibited excimer-type green emission from the stacked pyrene-center. The change in the Ln(III) ion promotes effective shifts of excimer emissions (Gd(III):500 nm, Eu(III):490 nm). The organic aggregation system using red-luminescent Eu(III) also provides temperature-sensitive ratiometric emission composed of π-π* and 4f-4f transitions by energy migration between aggregated ligands and Eu(III).

13.
Angew Chem Int Ed Engl ; 62(24): e202304591, 2023 Jun 12.
Artículo en Inglés | MEDLINE | ID: mdl-37040148

RESUMEN

Lanthanide upconversion luminescence in nanoparticles has prompted continuous breakthroughs in information storage, temperature sensing, and biomedical applications, among others. Achieving upconversion luminescence at the molecular scale is still a critical challenge in modern chemistry. In this work, we explored the upconversion luminescence of solution dispersions of co-crystals composed of discrete mononuclear Yb(DBM)3 Bpy and Eu(DBM)3 Bpy complexes (DBM: dibenzoylmethane, Bpy: 2,2'-bipyridine). The 613 nm emission of Eu3+ was observed under excitation of Yb3+ at 980 nm. From the series of molecular assemblies studied, the most intense luminescence was obtained for a 1 : 1 molar ratio of Yb3+ : Eu3+ , resulting in a high quantum yield of 0.67 % at 2.1 W cm-2 . The structure and energy transfer mechanism of the assemblies were fully characterized. This is the first example of an Eu3+ -based upconverting system composed of two discrete mononuclear lanthanide complexes present as co-crystals in non-deuterated solution.

14.
Foods ; 11(21)2022 Oct 27.
Artículo en Inglés | MEDLINE | ID: mdl-36360001

RESUMEN

In the present study, a lanthanide fluorescence sensor array was developed for the discrimination of honey's botanical origin. Dipicolinic acid (DPA) was used as the antenna ligand for sensitizing the fluorescence of Tb3+ and Eu3+ to prepare the DPA-Tb3+/Eu3+ complex. This lanthanide fluorescence sensor showed a cross-reactive response to the major constituents of honey, which led to the result that different classes of honey solution exhibited distinct quenching effects on the fluorescence of the DPA-Tb3+/Eu3+ complex. Furthermore, a fluorescence sensor array composed of ten sensors was constructed by adjusting the pH and the component of the DPA-Tb3+/Eu3+ complex to show multivariate responses towards honey. The visual fluorescence image of the sensor array was recorded by using a smartphone under excitation with portable UV lamp. Results indicated that the pattern of the visual image was related with the botanical origin. After extracting the RGB value of each sensor in 96-well plate, the ratio of R/G was used for principal component analysis (PCA). The results showed that three classes of honey (astragalus, logan, and litchi) were well distinguished. Moreover, the value of principal component 1 (PC1) showed good linearity with the composition of mixing honey and could be used for semi-quantitative analysis. The proposed lanthanide fluorescence sensor array presents a visual and portable method for the discrimination of a honey's origin without the use of analytical instruments, and might provide a novel and simple strategy for the measurement of food origin.

15.
Magn Reson Chem ; 60(10): 1005-1013, 2022 10.
Artículo en Inglés | MEDLINE | ID: mdl-35938541

RESUMEN

2 H solid-state nuclear magnetic resonance (NMR) is a method for examining the mobility and orientation of molecules in the field of biophysics. In studies on lipid bilayer membranes, 2 H NMR is often adopted to detect a phase transition from the gel to the liquid-crystal phase, which is observed as a change in spectral shape, and to evaluate the ordering of lipid alkyl chains using quadrupole coupling values. Because the mobility of membrane lipids is highly temperature dependent, precise temperature control is a prerequisite for evaluating the physical properties of membranes. Generally, NMR instruments monitor the temperature of the variable temperature (VT) gas. The temperature inside the sample tube and the VT gas match only when the heat generated by the radio frequency (rf) pulse emitted from the coil or magic angle spinning is significantly lower than the cooling capacity of the VT gas. In other words, the sample temperature inside the tube depends on the measurement method. Therefore, in this study, we took advantage of temperature-dependent changes in the chemical shift of a paramagnetic metal-ligand complex. We designed and synthesized a deuterated ligand complex and evaluated its temperature dependence as a thermometer for 2 H solid-state NMR spectroscopy. We chose Tb, Dy, Ho, and Er as the paramagnetic central metals. We then measured the 2 H NMR spectrum of each metal complex and confirmed the 2 H chemical shift to be temperature dependent. Furthermore, with the use of the thermometer molecule with Er, we succeeded in accurately evaluating the segmental melting of an alkyl chain in lipid bilayers with 0.1°C accuracy.


Asunto(s)
Membrana Dobles de Lípidos , Termómetros , Ligandos , Membrana Dobles de Lípidos/química , Espectroscopía de Resonancia Magnética/métodos , Lípidos de la Membrana , Temperatura
16.
Front Chem ; 10: 865447, 2022.
Artículo en Inglés | MEDLINE | ID: mdl-35464208

RESUMEN

Iron ion is widely present in the environment and in biological systems, and are indispensable trace elements in living organisms, so development of an efficient and simple sensor for sensing Fe(III) ions has attracted much attention. Here, six heterometallic AE-Ln coordination polymers (CPs) [Ln2 (pda)4(Hnda)2Ca2(H2O)2]·MeOH (Ln = Eu (1), Tb (2); H2pda = 2,6-pyridinedicarboxylic acid, H2nda = 2,3-naphthalenedicarboxylic acid), [Ln (pda)2 (nda)AE2(HCOO)(H2O)] (AE = Sr, Ln = Eu (3), Tb (4); AE = Ba, Ln = Eu (5), Tb (6)) with two-dimensional (2D) layer structures were synthesized by hydrothermal method. All of them were characterized by elemental analysis, XRD, IR, TG, as well as single crystal X-ray diffraction. They all show infinite 2D network structure, where complexes 1 and 2 are triclinic with space group of P 1 ¯ , while 3-6 belong to the monoclinic system, space group P21/n . The solid-state fluorescence lifetimes of complexes 1, 3 and 5 are τobs1 = 1930.94, 2049.48 and 2,413.04 µs, respectively, and the quantum yields Ф total are 63.01, 60.61, 87.39%, respectively, which are higher than those of complexes 2, 4 and 6. Complexes 1-6 all exhibited efficient fluorescence quenching response to Fe3+ ions in water, and were not interfered by the following metal ions: Cu2+, Cd2+, Mg2+, Ni2+, Co2+, Ca2+, Ba2+, Sr2+, Li+, Na+, K+, Al3+, Fe2+, Pb2+, Cr3+, Mn2+ and Zn2+. The quenching coefficient K SV for complexes 1-6 is 1.41 × 105 M-1, 7.10 × 104 M-1, 1.70 × 105 M-1, 1.57 × 105 M-1, 9.37 × 104 M-1, 1.27 × 105 M-1, respectively. The fluorescence quenching mechanism of these complexes towards Fe3+ ions was also investigated. It is possible that the weak interaction formed between the complexes and the Fe3+ ions reduce the energy transfer from the ligand to the Ln3+ ion, producing the emission burst effect. This suggests that complexes 1-6 can be candidate for efficient luminescent sensor of Fe3+.

17.
J Lumin ; 2322021 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-34565833

RESUMEN

Six dinuclear lanthanide(III) nitrato complexes [Ln(NO3)3(H2O)]2(µ-tppz) (where tppz = 2,3,5,6-tetra(2-pyridyl) pyrazine and Ln(III) = Nd (1), Sm (2), Eu (3), Gd (4), Tb (5), and Dy (6)) with bis-tridentate N-heterocyclic 2,3,5,6-tetra(2-pyridyl)pyrazine as bridging ligand have been solvothermally synthesized and characterized via elemental analysis, infrared spectroscopy, thermogravimetric analysis, single-crystal X-ray diffraction, and powder X-ray diffraction. The 3-D Hirshfeld surface and 2-D fingerprint plots show that the main interactions in 1-6 are the O⋯H/H⋯O intermolecular interactions with relative contributions of about 62%. Although the poor lanthanide(III)-centered luminescence properties clearly point to the efficiency of nonradiative quenching processes (presence of water molecules in the coordination sphere of the lanthanide(III) ions), the ligand tppz is better suited to sensitize the lanthanide(III)'s emissions of EuIII and NdIII than SmIII, TbIII, and DyIII. Finally, the magnetic data of DyIII comple×6 reveals antiferromagnetic coupling between DyIII ions.

18.
Anal Chim Acta ; 1181: 338905, 2021 Oct 09.
Artículo en Inglés | MEDLINE | ID: mdl-34556219

RESUMEN

Qualification and quantification of trace organic contaminants necessitates development of highly efficient sensing system, where excited-state inter-ligand proton transfer (ESILPT) provides a feasible pathway to construct efficient chemo-sensors. Herein, a strategically synthesized lanthanide complex, Eu(DBM)3(MeOH)3 (briefly as Eu-DBM-MeOH; DBM = dibenzoylmethane), features two-step ESILPT processes, along with modification on molecular structure and energy band. As a result, Eu-DBM-MeOH exhibits excellent photophysical properties with characteristic luminescence of Eu3+ ion. Benefiting from these merits, the Eu-DBM-MeOH complex acts as ultra-sensitive chemo-sensor toward nanomolar-level nitrofuran antibiotics (nitrofurazone and nitrofurantoin) in water, by disrupting ESILPT processes. Combining the advantages on photophysical property and luminescent sensitivity, ESILPT-active compounds are expected to widen and deepen the research on complex-based luminophores, being potentially useful in trace detection and biological imaging.


Asunto(s)
Elementos de la Serie de los Lantanoides , Nitrofuranos , Ligandos , Protones , Agua
19.
Appl Spectrosc ; 75(10): 1312-1319, 2021 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-34041959

RESUMEN

Melamine has been illegally adulterated in dairy food because of the rich nitrogen content and stable chemical properties in recent years. Therefore, the detection of melamine is of great significance for food safety supervision and human health protection. As melamine is a weak fluorescent substance, it is difficult to detect melamine directly by fluorescence spectroscopy. In this work, we found that melamine can significantly enhance the emission of the tetracycline-europium (EuTC) complex at 616 nm. Therefore, we took EuTC complex as a fluorescent probe to detect melamine. According to the characterizations of absorption spectra, molecular electrostatic potential distribution, and the time-resolved spectra, we speculated that tetracycline and melamine may form a complex through hydrogen bonding interaction in the melamine-EuTC reaction system, causing the melamine closer approach to Eu3+ and reducing the non-radiative energy loss of water molecules to Eu3+, which significantly enhanced the fluorescence intensity of EuTC. The fluorescence intensity of EuTC complex with melamine concentration in the range of 0.5-40.0 µM shows a good linear relationship, and the correlation coefficient is 0.9951 with the detection limit of 7.85 × 10-8 M. It shows a high sensitivity for the EuTC complex as a fluorescent probe to detect melamine, which provides a supplement and extension for the detection of melamine by fluorescence spectroscopy.


Asunto(s)
Colorantes Fluorescentes , Elementos de la Serie de los Lantanoides , Animales , Humanos , Límite de Detección , Leche/química , Espectrometría de Fluorescencia , Triazinas/análisis
20.
J Biomol Struct Dyn ; 39(14): 5105-5116, 2021 09.
Artículo en Inglés | MEDLINE | ID: mdl-32672500

RESUMEN

To investigate the chemotherapeutic and pharmacokinetic aspects of two lanthanide complexes (Tb(III) and La(III) containing 2,2'-bipyridine ligand), in vitro binding studies were carried out with BSA by employing multiple biophysical methods and molecular modeling study. There are different techniques containing fluorescence, absorption spectroscopy and competitive experiments to determine the interaction mode between BSA and these complexes. These complexes efficiently quenched the BSA emission through a static procedure. The results showed that the terbium and lanthanum complexes exhibited a high propensity for BSA interaction via van der Waals force. Further, competitive examination and docking study showed that the interaction site of these complexes on BSA is site III. The results of docking calculations were in good agreement with experimental examinations. Also, the energy transfer from BSA to these complexes has happened with high possibility. Moreover, antimicrobial studies of different bacterial and fungi indicated its promising antibacterial activity. In vitro cytotoxicity of the Tb complex and La complex was carried out in MCF-7 and A-549 cell lines, which revealed significantly good activity.Communicated by Ramaswamy H. Sarma.


Asunto(s)
Antiinfecciosos , Elementos de la Serie de los Lantanoides , 2,2'-Dipiridil/farmacología , Antiinfecciosos/farmacología , Sitios de Unión , Simulación del Acoplamiento Molecular , Unión Proteica , Albúmina Sérica Bovina/metabolismo , Espectrometría de Fluorescencia , Terbio , Termodinámica
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