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1.
Opt Lett ; 49(3): 415-417, 2024 Feb 01.
Artículo en Inglés | MEDLINE | ID: mdl-38300033

RESUMEN

We present a corrigendum to our Letter [Opt. Lett.48, 5699 (2023)10.1364/OL.505761]. In section 3 of the original supplementary material, the absolute value is incorrectly taken in resolving the Kubo formula for describing the conductivity of graphene. Because this is a mistake with the conductivity of graphene, the coupling of the original structure is broken when the correct result is inserted into the code of the transfer matrix. So, the structure of the arithmetic logic unit (ALU), characteristic frequency point, and phase control have been modified accordingly. However, the ultimate function and the conclusion of this work remain unchanged.

2.
Phys Chem Chem Phys ; 26(5): 4447-4454, 2024 Jan 31.
Artículo en Inglés | MEDLINE | ID: mdl-38240154

RESUMEN

A one-dimensional optical biosensing metastructure (OBM) with graphene layers is presented in this paper. It is realized by coherent perfect absorption (CPA) and operates in the transverse electric mode. It shows a strong linear fitting relationship between the refractive index (RI) of the analysis layer and the frequency corresponding to the absorption peak, and the R-square is up to 1. Additionally, based on the principle of CPA, the OBM can realize the function of multiple cancer cell detection by adjusting the detection range by controlling the phase difference of coherent electromagnetic waves. Its detection ranges are 1.34-1.355 and 1.658-1.662. Thanks to its high-quality factor, great figure of merit, and low detection limit, whose best values are, respectively, 6.9 × 104, 1.2 × 104 RIU-1, and 3.6 × 10-6 RIU, the detection of weak changes in the RI of a cancer cell is possible. Additionally, its sensitivity can reach 26.57 THz RIU-1. This OBM based on CPA has major implications for advancing the study and investigation into the application of CPA. It also provides a simple and efficient approach to distinguish cancer cells and may be widely used in the biomedical field.


Asunto(s)
Grafito , Neoplasias , Humanos , Electricidad , Neoplasias/diagnóstico
3.
BMC Endocr Disord ; 24(1): 108, 2024 Jul 10.
Artículo en Inglés | MEDLINE | ID: mdl-38982394

RESUMEN

OBJECTIVE: We aimed to analyze the relationship between non-alcoholic fatty liver and progressive fibrosis and serum 25-hydroxy vitamin D (25(OH)D) in patients with type 2 diabetes mellitus. METHODS: A total of 184 patients with T2DM who were hospitalized in the Department of Endocrinology of the ShiDong Clinical Hospital between January 2023 and June 2023 were selected. We compared review of anthropometric, biochemical, and inflammatory parameters and non-invasive scores between groups defined by ultrasound NAFLD severity grades.We determine the correlation between 25(OH)D and FLI and FIB-4 scores, respectively. RESULTS: Statistically significant differences were seen between BMI, WC, C-peptide levels, FPG, ALT, serum 25(OH)D, TC, HDL, lumbar spine bone density, FLI, and FIB-4 in different degrees of NAFLD. Multivariate logistic regression analysis showed that 25(OH)D (OR = 1.26, p = 0.001), age (OR = 0.93, P < 0.001) and BMI (OR = 1.04, p = 0.007) were independent predictors of NAFLD in patients with T2DM. CONCLUSIONS: This study revealed the correlation between serum 25(OH)D levels and NAFLD in patients with T2DM. We also demonstrated that serum 25(OH)D levels were negatively correlated with FLI/FIB-4 levels in patients with T2DM with NAFLD, suggesting that vitamin D deficiency may promote hepatic fibrosis progression in T2DM with NAFLD.


Asunto(s)
Diabetes Mellitus Tipo 2 , Cirrosis Hepática , Enfermedad del Hígado Graso no Alcohólico , Vitamina D , Humanos , Enfermedad del Hígado Graso no Alcohólico/sangre , Enfermedad del Hígado Graso no Alcohólico/complicaciones , Enfermedad del Hígado Graso no Alcohólico/patología , Diabetes Mellitus Tipo 2/sangre , Diabetes Mellitus Tipo 2/complicaciones , Femenino , Masculino , Vitamina D/sangre , Vitamina D/análogos & derivados , Persona de Mediana Edad , Cirrosis Hepática/sangre , Cirrosis Hepática/patología , Anciano , Progresión de la Enfermedad , Biomarcadores/sangre , Deficiencia de Vitamina D/sangre , Deficiencia de Vitamina D/complicaciones , Deficiencia de Vitamina D/epidemiología , Pronóstico , Adulto , Estudios de Seguimiento
4.
Anal Chem ; 95(11): 4992-4999, 2023 03 21.
Artículo en Inglés | MEDLINE | ID: mdl-36877827

RESUMEN

A lanthanide-based three-dimensional metal-organic framework with excellent water, acid/base, and solvent stability, namely {[(CH3)2NH2]0.7[Eu2(BTDBA)1.5(lac)0.7(H2O)2]·2H2O·2DMF·2CH3CN}n (JXUST-29, H4BTDBA = 4',4‴-(benzo[c][1,2,5]thiadiazole-4,7-diyl)bis([1,1'-biphenyl]-3,5-dicarboxylic acid), Hlac = lactic acid), has been synthesized and characterized. Since the N atoms of the thiadiazole group will not coordinate with lanthanide ions, JXUST-29 has a free basic N-site accessible to small H+ ions, which allows it to be used as a promising pH fluorescence sensor. Interestingly, the luminescence signal was significantly enhanced, with an approximately 54-fold enhancement in the emission intensity when the pH value was increased from 2 to 5, which is the typical behavior of pH probes. In addition, JXUST-29 can also be used as a luminescence sensor to detect l-arginine (Arg) and l-lysine (Lys) in an aqueous solution through fluorescence enhancement and the blue-shift effect. The detection limits were 0.023 and 0.077 µM, respectively. In addition, JXUST-29-based devices were designed and developed to facilitate detection. Importantly, JXUST-29 is also capable of detecting and sensing Arg and Lys in living cells.


Asunto(s)
Elementos de la Serie de los Lantanoides , Estructuras Metalorgánicas , Estructuras Metalorgánicas/química , Lisina , Elementos de la Serie de los Lantanoides/química , Iones , Agua/química , Concentración de Iones de Hidrógeno
5.
Opt Lett ; 48(21): 5699-5702, 2023 Nov 01.
Artículo en Inglés | MEDLINE | ID: mdl-37910737

RESUMEN

An arithmetic logic unit (ALU) based on the metastructure (MS) with coherent absorption (CA) is proposed in this Letter. The ALU can perform AND and exclusive OR logical operations at the same frequency point. So it can be regarded as an optical half-adder. By controlling the chemical potential of graphene and the phase difference of coherent electromagnetic waves (EWs), two different binary numbers are input into the ALU. The dynamic absorption peaks, which are generated based on the CA, output the outcomes of the carry-digit bit and non-carry sum bit. This ALU can be used in the field of optical processing and encryption, such as processing hamming code. This given ALU based on the MS with CA has major implications for advancing the study and investigation into the application of CA. Furthermore, it also provides a new, to the best of our knowledge, idea for the study of MS with logical operation.

6.
Chemistry ; 29(38): e202300598, 2023 Jul 06.
Artículo en Inglés | MEDLINE | ID: mdl-37062699

RESUMEN

Multifunctional materials with working temperatures near room temperature are crucial for practical applications. Until now, it is still a great challenge to obtain such materials. In this paper, a complex of (C5 NH13 Cl)2 MnBr4 (1) with a structural phase transition near room temperature is reported. The phase transition induces switchable magnetic properties, dielectric anomalies and luminescent response over the same range of temperatures. It is the first time the synergetic effect of magnetism, dielectricity and luminescence near room temperature have been observed in the same molecular complex.


Asunto(s)
Luminiscencia , Magnetismo , Temperatura , Transición de Fase
7.
Inorg Chem ; 62(16): 6255-6262, 2023 Apr 24.
Artículo en Inglés | MEDLINE | ID: mdl-37026758

RESUMEN

An aqueous stable europium-based metal-organic framework with properties of ratiometric fluorescence sensing, namely, {[(CH3)2NH2][Eu(TCPB)(H2O)2]·DMF}n (Eu-MOF; H4TCPB = 1,2,4,5-tetrakis(4-carboxyphenyl)-benzene), was synthesized under solvothermal conditions and structurally characterized. Crystal structure analysis shows that Eu-MOF is a three-dimensional porous crystal, in which the EuIII ion is an eight-coordinate square inverse prism with eight oxygen atoms. Fluorescence measurements show that Eu-MOF exhibits characteristic emission of the EuIII ion and ligand. Eu-MOF displays good selectivity and sensitivity as a ratiometric fluorescence sensor for phosphate anions with a low detection limit in Tris-HCl buffer solution. Furthermore, Eu-MOF also has a good ability to identify salicylaldehyde through fluorescence quenching with a detection limit of 0.095 ppm. Therefore, it is an excellent fluorescent sensing material for phosphate and organic salicylaldehyde.

8.
Inorg Chem ; 62(29): 11510-11517, 2023 Jul 24.
Artículo en Inglés | MEDLINE | ID: mdl-37424076

RESUMEN

The unraveling of the stimuli-responsive mechanism is crucial to the design and precise synthesis of stimuli-responsive luminescent materials. We report herein the mechanochromic and selective vapochromic solid-state luminescence properties of a new bimetallic cuprous complex [{Cu(bpmtzH)}2(µ-dppm)2](ClO4)2 (1), and the corresponding response mechanisms are elucidated by investigating its two different solvated polymorphs 1·2CH2Cl2 (1-g) and 1·2CHCl3 (1-c). Green-emissive 1-g and cyan-emissive 1-c can be interconverted upon alternate exposure to CHCl3 and CH2Cl2 vapors, which is principally attributable to a combined alteration of both intermolecular NHbpmtzH···OClO3- hydrogen bonds and intramolecular "triazolyl/phenyl" π···π interactions induced by different solvents. Solid-state luminescence mechanochromism present in 1-g and 1-c is mainly ascribed to the grinding-induced breakage of the NHbpmtzH···OClO3- hydrogen bonds. It is suggested that intramolecular π···π-triazolyl/phenyl interactions are affected by different solvents but not by grinding. The results provide new insights into the design and precise synthesis of multi-stimuli-responsive luminescent materials by the comprehensive use of intermolecular hydrogen bonds and intramolecular π···π interactions.

9.
Inorg Chem ; 62(43): 17993-18001, 2023 Oct 30.
Artículo en Inglés | MEDLINE | ID: mdl-37844614

RESUMEN

Four new isostructural rare earth metal-organic frameworks (RE-MOFs) were synthesized and full characterized, namely, {[(CH)2NH2]3[RE2(BTDBA)2(HCOO)]·5H2O·2DMF}n (H4BTDBA = (4',4'''-(benzo[c][1,2,5]thiadiazole-4,7-diyl)bis([1,1'-biphenyl]-3,5-dicarboxylic acid); RE = Eu (JXUST-34), Gd (JXUST-35), Tb (JXUST-36), and Dy (JXUST-37)). The single-crystal structures analysis shows that JXUST-34-37 are chain-based three-dimensional structures. Importantly, JXUST-34 exhibits excellent water, organic solvents, and acid-base stability, which can be used as a fluorescence sensor for folic acid and Al3+ with detection limits of 0.02 mM and 0.05 µM, respectively. The presence of free [(CH)2NH2]+ cations in the channels can engage the proton carrier during proton conduction. JXUST-34-37 display good proton conductivity, and the conductivities vary with relative humidity and temperatures, among which JXUST-37 has the highest conductivity of 9.66 × 10-3 S·cm-1 at 60 °C and 98% RH. The magnetic studies show that the -ΔSm of JXUST-35 reaches 16.13 J kg-1 K-1 at 2 K and ΔH = 7 T. JXUST-34-37 show multifunctional properties of fluorescence sensing, high proton conductivity, and magnetic refrigeration, which provides a new clue for the development of fluorescent-responsive, magnetic-refrigerant, and proton-conductive RE-MOF materials.

10.
Inorg Chem ; 62(51): 21322-21328, 2023 Dec 25.
Artículo en Inglés | MEDLINE | ID: mdl-38071665

RESUMEN

Lanthanide-based metal-organic frameworks show good potential for applications due to their unique structures and functional properties. A highly thermally and acid-base stable Eu-MOF was synthesized by a solvothermal method with the molecular formula {[(CH3)2NH2]2[Eu2(NDDP)2(H2O)2]·H2O}n (Eu-MOF, H4NDDP = 5,5'-(naphthalene-2,6-diyl)diisophthalic acid). Eu-MOF takes a three-dimensional (4,4,8)-connected topology. The water molecules involved in the coordination, free water molecules, and [(CH3)2NH2]+ cations in the pore can be used as proton carriers. The proton conductivity attains 1.25 × 10-4 S cm-1 at room temperature and 2.42 × 10-3 S cm-1 at 70 °C and 98% relative humidity. Combined with the dual-emission properties from the ligands and Eu(III) ions enables Eu-MOF to be used as a ratiometric fluorescent sensor for phosphate efficiently and rapidly, with a limit of detection of 0.12 µM in the Tris-HCl buffer solution. These results provide a new approach for the construction of MOFs with high proton conductivity and a ratiometric fluorescence response.

11.
Inorg Chem ; 62(30): 12001-12008, 2023 Jul 31.
Artículo en Inglés | MEDLINE | ID: mdl-37452746

RESUMEN

A europium(III) metal-organic framework (MOF), namely, {[[(CH3)2NH2]3Eu2(DTTP-2OH)2(HCOO)(H2O)]·4H2O}n (Eu-MOF, H4DTTP-2OH = 2',5'-dihydroxy-[1,1':4',1″-terphenyl]-3,3″,5,5″-tetracarboxylic acid) has been assembled through solvothermal method. The Eu-MOF is a three-dimensional (3D) (4,4,8)-connected topological framework with binuclear Eu(III) clusters as secondary building units, in which a richly ordered hydrogen bonding network formed among the free H2O molecules, dimethylamine cations, and phenolic hydroxyl groups provides a potential pathway for proton conduction. The proton conductivity reaches the category of superionic conductors (σ > 10-4 S cm-1) at room temperature with a maximum conductivity of 1.91 × 10-3 S cm-1 at 60 °C and 98% RH. Moreover, it also can be used as a fluorescence sensor in aqueous solution with detection limits of 0.14 µM for tetracycline, 0.13 µM for oxytetracycline and 0.11 µM for doxycycline. These results pave new methods for constructing MOFs with high proton conductivity and responsive fluorescence.

12.
Inorg Chem ; 62(6): 2760-2768, 2023 Feb 13.
Artículo en Inglés | MEDLINE | ID: mdl-36724472

RESUMEN

A stable metal-organic framework with the formula {[Co(BBZB)(IPA)]·H2O}n (JXUST-23, BBZB = 4,7-bis(1H-benzimidazole-1-yl)-2,1,3-benzothiadiazole and H2IPA = isophthalic acid) was constructed by incorporating Co2+ ions and two conjugated ligands under solvothermal conditions. JXUST-23 takes a dinuclear cluster-based layer structure with a porosity of 2.7%. In this work, JXUST-23 was used to activate peroxymonosulfate (PMS) to degrade rhodamine B (RhB), a difficult-to-degrade pollutant in water. Compared with pure PMS or JXUST-23, the JXUST-23/PMS system displays the best degradation ability of RhB in neutral solution. When the mass ratio of JXUST-23 to PMS was 2:3, 99.72% of RhB (50 ppm) was removed within 60 min, and the reaction rate was 0.1 min-1. Furthermore, free radical quenching experiments show that SO4•- was the main free radical during the process of RhB degradation. In addition, JXUST-23 exhibits good reusability for the degradation of the organic dye RhB, making it a potential candidate for environmental remediation.

13.
Inorg Chem ; 62(9): 3799-3807, 2023 Mar 06.
Artículo en Inglés | MEDLINE | ID: mdl-36808965

RESUMEN

Two novel lanthanide metal-organic frameworks (MOFs) with the formulas [Tb(bidc)(Hbidc)(H2O)]n (JXUST-20) and {[Tb3(bidc)4(HCOO)(DMF)]·solvents}n (JXUST-21) were synthesized based on 2,1,3-benzothiadiazole-4,7-dicarboxylic acid (H2BTDC) under solvothermal conditions. Interestingly, benzimidazole-4,7-dicarboxylic acid (H2bidc) was formed in situ using H2BTDC as the starting material. The self-assembly process of the targeted MOFs with different topological structures can be controlled by the solvents and concentration of the reactants. Luminescence experiments show that JXUST-20 and JXUST-21 exhibit strong yellow-green emission. JXUST-20 and JXUST-21 can selectively sense benzaldehyde (BzH) via a luminescence quenching effect with detection limits of 15.3 and 1.44 ppm, respectively. In order to expand the practical application of MOF materials, mixed-matrix membranes (MMMs) have been constructed by mixing targeted MOFs and poly(methyl methacrylate) in a N,N-dimethylformamide (DMF) solution, which can also be used for BzH vapor sensing. Therefore, the first case of MMMs derived from TbIII MOFs has been developed for the reversible detection of BzH vapor, providing a simple and efficient platform for the future detection of volatile organic compounds.

14.
Environ Sci Technol ; 57(51): 21767-21778, 2023 Dec 26.
Artículo en Inglés | MEDLINE | ID: mdl-38096549

RESUMEN

The anoxic zone serves as the core functional unit in municipal wastewater treatment plants (MWWTPs). Unfortunately, in most cases, the downstream range of the anoxic zone is severely lacking in available organic carbon and thus contributes little to the removal of nutrients. This undesirable range is termed the "carbon-restricted anoxic zone", representing an insurmountable drawback for traditional MWWTPs. This study uncovers a previously overlooked role for the carbon-restricted anoxic zone: a hotspot for anaerobic ammonium oxidation (anammox). In a continuous-flow pilot-scale plant treating municipal wastewater (55 m3/d), virgin biocarriers were introduced into the carbon-restricted anoxic zone (downstream 25% of the anoxic zone with BOD5 of 5.9 ± 2.3 mg/L). During the 517-day monitoring, anammox bacteria highly self-enriched within the biofilms, with absolute and relative abundance reaching up to (9.4 ± 0.1) × 109 copies/g-VSS and 6.17% (Candidatus Brocadia), respectively. 15N isotopic tracing confirmed that anammox overwhelmingly dominated nitrogen metabolism, responsible for 92.5% of nitrogen removal. Following this upgrade, the contribution ratio of the carbon-restricted anoxic zone to total nitrogen removal increased from 9.2 ± 4.1% to 19.2 ± 4.2% (P < 0.001), while its N2O emission flux decreased by 84.5% (P < 0.001). These findings challenge stereotypes about the carbon-restricted anoxic zone and highlight the multiple environmental implications of this newfound anammox hotspot.


Asunto(s)
Carbono , Purificación del Agua , Oxidación Anaeróbica del Amoníaco , Reactores Biológicos/microbiología , Oxidación-Reducción , Nitrógeno/metabolismo
15.
Phys Chem Chem Phys ; 25(32): 21456-21467, 2023 Aug 16.
Artículo en Inglés | MEDLINE | ID: mdl-37539623

RESUMEN

Based on cylindrical photonic crystals in one dimension, a multi-scale sensor device with a logic operation is being proposed. At the same time, it can satisfy the functions of refractive index (RI) and magnetic field detection. Under the modulation of an external magnetic field, sharp absorption peaks (APs) are obtained in the terahertz (THz) range. In a certain frequency range (AP value above 0.9), as the particular InSb layers are applied to two different magnetic fields, APs of the same frequency can be implemented to operate as XOR logic gates. The results show that with a change in the detected physical quantity, the frequency point of the corresponding AP also moves. Therefore, by adjusting the position of the AP, the magnetic field and RI can be sensed, and the device shows relatively excellent performance of 6879.88 and 6943.65 in terms of quality factor. In addition, the optimal performance of sensitivity, detection limit, and corresponding figure of merit is 0.01264(2πc/d0) T-1, 2.25 × 10-4 T, 227.23 T-1, and -0.003779(2πc/d0) RIU-1, 7.69 × 10-3 RIU, 67.74 RIU-1. In terms of overall sensors, the proposed device is highly innovative in structure and meets the requirements of multi-scale measurements.

16.
Molecules ; 28(22)2023 Nov 09.
Artículo en Inglés | MEDLINE | ID: mdl-38005227

RESUMEN

Multifunctional materials with a coexistence of proton conduction properties, single-molecule magnet (SMM) behaviors and magneto-optical Faraday effects have rarely been reported. Herein, a new pair of Cu(II)-Dy(III) enantiomers, [DyCu2(RR/SS-H2L)2(H2O)4(NO3)2]·(NO3)·(H2O) (R-1 and S-1) (H4L = [RR/SS] -N,N'-bis [3-hydroxysalicylidene] -1,2-cyclohexanediamine), has been designed and prepared using homochiral Schiff-base ligands. R-1 and S-1 contain linear Cu(II)-Dy(III)-Cu(II) trinuclear units and possess 1D stacking channels within their supramolecular networks. R-1 and S-1 display chiral optical activity and strong magneto-optical Faraday effects. Moreover, R-1 shows a zero-field SMM behavior. In addition, R-1 demonstrates humidity- and temperature-dependent proton conductivity with optimal values of 1.34 × 10-4 S·cm-1 under 50 °C and 98% relative humidity (RH), which is related to a 1D extended H-bonded chain constructed by water molecules, nitrate and phenol groups of the RR-H2L ligand.

17.
Opt Lett ; 47(23): 6065-6068, 2022 Dec 01.
Artículo en Inglés | MEDLINE | ID: mdl-37219173

RESUMEN

A non-reciprocity sensor based on a layered structure with multitasking is proposed, which realizes biological detection and angle sensing. Through an asymmetrical arrangement of different dielectrics, the sensor obtains non-reciprocity on the forward and backward scales, thus achieving multi-scale sensing in different measurement ranges. The structure sets the analysis layer. Injecting the analyte into the analysis layers by locating the peak value of the photonic spin Hall effect (PSHE) displacement, cancer cells can accurately be distinguished from normal cells via refractive index (RI) detection on the forward scale. The measurement range is 1.569∼1.662, and the sensitivity (S) is 2.97 × 10-2 m/RIU. On the backward scale, the sensor is able to detect glucose solution with 0∼400 g/L concentrations (RI = 1.3323∼1.38), with S = 1.16 × 10-3 m/RIU. When the analysis layers are filled with air, high-precision angle sensing can be achieved in the terahertz range by locating the incident angle of the PSHE displacement peak; 30°âˆ¼45°, and 50°âˆ¼65° are the detection ranges, and the highest S can reach 0.032 THz/°. This sensor contributes to detecting cancer cells and biomedical blood glucose and offers a new way to the angle sensing.

18.
Inorg Chem ; 61(40): 16177-16184, 2022 Oct 10.
Artículo en Inglés | MEDLINE | ID: mdl-36149649

RESUMEN

A new polydentate tetracarboxylic acid with a benzothiadiazole unit (4',4'''-(benzo[c][1,2,5]thiadiazole-4,7-diyl)bis([1,1'-biphenyl]-3,5-dicarboxylic acid), H4BTDBA) has been used to prepare a pH-stable three-dimensional TbIII-based metal-organic framework (MOF) with the formula {[(CH3)2NH2]0.7[Tb2(BTDBA)1.5(lac)0.7(H2O)2]·solvents}n (Hlac = lactic acid, JXUST-19). JXUST-19 exhibits a new (4,4,12)-connected topology based on tetranuclear [Tb4] clusters. JXUST-19 can remain stable when soaked in water for at least 1 week and in aqueous solutions with various pH values (2-12) for 24 h. Fluorescence study indicates JXUST-19 can be employed as a rare turn-on and blue-shift MOF sensor toward benzaldehyde (BZ) and salicylaldehyde (SA). To date, JXUST-19 represents the first TbIII-based turn-on MOF sensor toward salicylaldehyde in aqueous solution, and the fluorescence enhancement and naked-eye detection of BZ have been rarely reported. In addition, JXUST-19 based fluorescent test papers, light-emitting diode lamp beads, and portable composite films were developed to realize naked-eye detection of BZ and SA, which has great potential in practical applications.

19.
Inorg Chem ; 61(18): 6819-6828, 2022 May 09.
Artículo en Inglés | MEDLINE | ID: mdl-35475364

RESUMEN

Four new isostructural lanthanide metal-organic frameworks (MOFs), namely {[Ln(DMTP-DC)1.5(H2O)3]·DMF}n [H2DMTP-DC = 2',5'-dimethoxytriphenyl-4,4″-dicarboxylic acid; LnIII = EuIII (1), GdIII (2), TbIII (3), and DyIII (4)], have been synthesized and characterized. Single-crystal structure analysis reveals that 1-4 are three-dimensional Ln-MOFs with rich H-bonding of coordinated H2O molecules in the network channels. The X-ray diffraction patterns indicate that Ln-MOF 1 displays good stabilities in organic solvents and aqueous solutions with distinct pH values. Both 1 and 3 show characteristic emission of LnIII ions. Ln-MOF 1 can be used as a ratiometric fluorescence sensor for arginine and lysine in aqueous solution, and the detection limits are 24.38 µM for arginine and 9.31 µM for lysine. All 1-4 show proton conductivity related to relative humidity (RH) and temperature, and the maximum conductivity values of 1-4 at 55 °C and 100% RH are 9.94 × 10-5, 1.62 × 10-4, 1.71 × 10-4, and 2.67 × 10-4 S·cm-1, respectively. The value of σ increases with the decrease in ionic radius, indicating that the radius of the LnIII ions can regulate the proton conductivity of these MOFs. Additionally, 2 exhibits a significant magnetocaloric effect (MCE) with a magnetic entropy change (-ΔSm) of 18.86 J kg-1 K-1 for ΔH = 7 T at 2 K, and 4 shows weak field-induced slow relaxation of magnetization. The coexistence of good fluorescence sensing capability, attractive proton conductivity, and relatively large MCE in Ln-MOFs is rare, and thus, 1-4 are potentially multifunctional MOF materials.


Asunto(s)
Elementos de la Serie de los Lantanoides , Estructuras Metalorgánicas , Aminoácidos , Arginina , Fluorescencia , Elementos de la Serie de los Lantanoides/química , Lisina , Estructuras Metalorgánicas/química , Protones , Agua
20.
Inorg Chem ; 61(1): 254-264, 2022 Jan 10.
Artículo en Inglés | MEDLINE | ID: mdl-34951312

RESUMEN

An in-depth study on a stimuli-responsive tetranuclear cuprous luminescent complex is reported and gives new insights into the origin and possible use of the observed stimuli-responsive luminescence. Its crystalline polymorphs with two different shapes are obtained by using different crystallization solvents and show distinct emissions, with one being blue emissive and the other being yellow emissive. Upon grinding, only the blue-emitting polymorph has a marked change in the emission color from blue to yellow, and its ground sample exhibits a yellow emission similar to that of the yellow-emitting polymorph. Interestingly, the yellow-emitting polymorph after exposure to acetone vapor can emit a blue emission and display luminescence mechanochromism similar to that of the blue-emitting polymorph. Single-crystal structural analyses of the two different polymorphs reveal the relationship between the mechanochromic luminescence and the geometrical configuration of the {Cu(µ-dppm)2Cu} unit and intramolecular "pyridyl/phenyl" π···π interactions, supported as well by their PXRD, FT-IR, TGA, and PL studies in various states and by TD-DFT analyses. The results demonstrate the different roles of switchable intramolecular π···π interactions and the geometrical configuration of the {Cu(µ-dppm)2Cu} unit in this stimuli-responsive luminescence and potential applications of such stimuli-responsive luminescence in optical sensing and anticounterfeiting encryption technologies and deepen the understanding of such stimuli-responsive luminescence originating from switchable intramolecular π···π interactions. In addition, it is clearly suggested that the rational utilization of switchable intramolecular π···π interactions is a feasible route for developing stimuli-responsive intelligent luminescent materials and devices.

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