Metal-organic frameworks (MOFs), as a class of crystalline organic-inorganic hybrid materials, have demonstrated excellent performance in many fields, resulting in attracting more and more attention. Recently, MOFs have been widely used as functional materials to immobilize aptamers via various interaction forces. The MOF-based aptasensors exhibit outstanding sensing performance, including high sensitivity, excellent selectivity, and good designability, by utilizing the advantages of MOFs and aptamers. Developing MOF-based aptasensors is gradually becoming one of the important research hotspots. Herein, a comprehensive review of aptasensors based on MOFs is provided to summarize recent advancements in this field. Some representative examples are discussed in detail. Furthermore, opportunities and challenges in this field are proposed in this review.
A novel dendritic DNA-quantum dot (QD) electrochemiluminescence (ECL) probe was developed and an ECL biosensor constructed for sensitive detection of Hg2+ in water samples by combining with enzyme-assisted multiple cycle amplification strategy. Firstly, the Y-shaped structure was formed based on the Hg2+-induced enzymatic cycle amplification technique, which improved the cutting efficiency and realized the double-amplified DNA product. Moreover, a unique dendritic DNA nanostructure loading numerous QDs was constructed, which can greatly amplify the ECL signal. After the dendritic DNA signal probe was connected to the CNT/gold nanocomposites/electrode by DNA products, the ECL biosensor was constructed for sensitive detection of Hg2+. The proposed dendritic DNA probe opens new ECL application of quantum dots. The smart design of Y-structure coupled with multiple amplification strategy greatly improves detection accuracy and sensitivity; thus, the biosensor not only can detect Hg2+ in water samples, but also has a good application prospect for other targets in environmental analysis.
Metal–organic frameworks (MOFs) have received lots of attention in the field of electrochemical aptasensors in recent years, but most MOFs have poor conductivity to limit their electrochemical detection performance. Hence, it is still a great challenge to construct excellent MOF-based composites for fabricating outstanding electrochemical aptasensors. In this work, a zirconium–organic framework (PCN-222) is assembled with the MXene nanosheet to obtain a PCN-222@MXene nanocomposite. Due to copious Zr(IV) sites and abound mesopores of PCN-222, and the good conductivity of MXene nanosheets, the PCN-222@MXene nanocomposite is a good functional material to immobilize aptamers. Oxytetracycline (OTC), as an analytic mode, has been widely used in various applications, but the residual OTC brings a series of health and environmental problems. Excitingly, the electrochemical aptasensor based on PCN-222@MXene exhibits more outstanding sensing performance toward OTC via differential pulse voltammetry than many reported sensors, including low limitation of detection, high selectivity, available stability and reproducibility.
MOF-based materials, as bifunctional catalysts for electrocatalytic water splitting, play an important role in the application and development of clean fuel hydrogen energy. This study presents a series of novel 3D Co-based MOFs with layered networks, including [Co(4,4 '-bipy)(0.5)(aip)(CH3OH)H2O](n) (Co-MOF 1), [Co-2(1,3 '-bit)(aip)(2)(CH3OH)H2O](n) (Co-MOF 2), [Co(4,4 '-bipb)(aip)](n) (Co-MOF 3), and [Co-2(4,4 '-bipe)(aip)(2)1.5H(2)O](n) (Co-MOF 4). Their single-crystal structures of Co-MOFs 1-4 are characterized and analyzed before being applied in alkaline solutions for water decomposition (OER and HER). The electrocatalytic tests indicate that Co-MOFs 1-4 exhibit a good performance. Notably, Co-MOF 4 exhibits great behavior which has low overpotentials of 94 and 188 mV (OER) as well as 185 and 352 mV (HER) at the currents of 10 and 100 mA cm(-2), respectively. In comparison with Co-MOFs 1-3, Co-MOF 4 has the lowest Tafel slopes, highest ECSA, and smallest resistance. The immanent qualities, such as distinct interwoven long chain layered structure, unsaturated coordination modes, and synergistic catalytic qualities among Co ions, contribute to explaining the results. The fundamentals provide valuable information for the investigation of innovative MOF-based bifunctional electrocatalysts for overall water splitting.
Metal-organic frameworks (MOFs), as a class of functional porous materials, have gained extensive attention for constructing excellent electrochemical aptasensors. To overcome the insufficient conductivity of MOF materials, various conductive materials are gradually applied to assemble with MOFs. At present, the construction of sensitive MOF hybrid material-based electrochemical aptasensor is still significant importance. In this work, a hybrid material, namely MOF-74(Mg)/GO, is successfully synthesized by the in situ assembly of MOF-74(Mg) and graphene oxide (GO). The as-synthesized composite possesses the advantages of MOF-74(Mg) and GO, resulting in the fabricated electrochemical aptasensor with excellent detection performance toward ultra-trace streptomycin via electrochemical impedance spectroscopy.
The synthesis and characterization of two new porphyrin-based porous organic polymers (POPs) via Sonogashira cross-coupling reaction and leverage the two obtained POPs is reported for the fabrication of electrochemical aptasensors to detect kanamycin at an ultratrace level. The resultant electrochemical aptasensor demonstrates a high linear relationship with the logarithmic value of kanamycin concentration in the range 5 × 10 −5 –5 μg/L with the limit of detection of 17.6 pg/L or 36.3 fM. During the analysis of real samples from milk and river, a relative standard deviation of less than 4.39%, and good recovery values in the range 97.0–105% were obtained. Graphical Abstract
Multidentate ligands can be used to construct structurally adjustable metal-organic framework materials due to their abundant coordination sites. MOFs 1 - 4 with different configurations are synthesized by solvothermal method based on the symmetrical tetracarboxylic acid H4L main ligand (H4L = 5 '-(4-carboxyphenyl)-[1,1 ':2 ',1 ''- terphenyl]-4,4 ',4 ''-tricarboxylic), named [Co2(L)(bimb)]n (MOF 1, bimb=(1,1 '-(1,4-butanediyl) bis (imidazole)), [Co2(L)(bix)]n, (MOF 2, bix=1,4-bis(imidazol-1-ylmethyl) benzene), [Co4(L)2(bidpe)2]n (MOF 3, bidpe=4,4 '- bis(imidazolyl)diphenyl ether) and {[Co4(L)(bibdp)2(C3H7NO)]& sdot;2(C3H7NO)}n (MOF 4, bibdp=4,4 '-bis(1-imi- dazolyl) biphenyl), respectively. The rich coordination sites of H4L carboxylic acid ligands bring diverse coordination modes, forming Co2N2O8 secondary construction units. Based on it, MOFs 1 - 4 exhibits pillar-layered 3D porous supramolecular structure. Electrochemical measurements support that MOFs 1 - 4 exhibits excellent OER (oxygen evolution reaction) and HER (hydrogen evolution reaction) activities, especially MOF 3, which only requires overpotentials of 180 and 196 mV to reach the current density of 10 mA & sdot;cm- 2. Remarkable catalytic performance of MOF 3 is attributed to the abundant and dispersed reactive active sites brought by the 3D interpenetrated structure assembled based on tetranuclear metal clusters. The HER occurs through VolmerHeyrovsky mechanism, meanwhile, possible mechanisms of OER have been predicted. This investigation provides inspiration for exploring multi-core structured MOF materials as efficient HER/OER bifunctional catalysts for electrolytic overall water splitting.
The proposal of the dual-carbon target has attracted widespread attention to explore hydrogen evolution reaction (HER) electrocatalysts to promote the development of clean energy. Here, we propose a strategy to form hierarchically porous electrocatalytic hydrogen evolution catalysts (MOFs I-II) by calcining prefabricated Ni-metal-organic frameworks (MOFs 1 - 2) under N-2 atmosphere. Among them, three-dimensional (3D) porous MOFs 1 - 2 have been synthesized by solvothermal method based on scissor-shaped tetracarboxylic acid, named {[Ni-2(L)(1,3-bit)(H2O)(3)](C2H3N)}(n) (MOF 1) and [Ni-4(tib)(L)(2)(H2O)(3)(mu(2)-O)](n) (MOF 2). Single crystal diffraction analysis shows that MOF 1 is 3,4,7-connected 3-nodes 3D framework composed of two kinds 2D planes, while MOF 2 is 2,4,7-connected 3-nodes 3D supramolecular structure constructed from 1D chains and 2D planes. As expected, SEM and BET analysis show that calcination produced a unique hierarchical micro-mesoporous structure, while the specific surface area increases by 2.3-3.8 times. The optimized MOF II exposes more active sites, accelerates electrolyte ion diffusion, and has lower electron transfer resistance, allowing it to exhibit excellent electrocatalytic HER performance in an alkaline environment. Notably, MOF II has a Tafel slope of 81 mVdec(-1) (10 mAcm(-2)) with a lower overpotential (225 mV). Compared with the pristine MOF 2, the performance of MOF II is significantly improved and it can operate stably for a long time. The possible electrocatalytic HER mechanism has been investigated by density functional theory (DFT). The results are expected to provide inspiration for the rational design and development of stable and efficient MOF-based HER electrocatalysts.
Presented here is a photoactive cluster-organic frameworks with 1D Cu-I chain, namely (Cu2I)(pytz) (1) (Hpytz = 5-(4 '-pyridyl)tetrazole). Compound 1 features a unique 1D Cu-I chain constructed from a Cu3I2 cluster. These chains are interconnected by the tetrazole moiety of pytz, forming a 2D layer. Furthermore, the pyridine moiety of pytz acts as pillars, creating a pillar-layered framework. Moreover, compound 1 displays strong photoluminescence, excellent visible light adsorption, and remarkable photocatalytic activity for the degradation of methylene blue under visible light conditions. These properties highlight the potential applications of these frameworks in areas such as optoelectronics and environmental remediation.
In this work, a fluorescent probe N with aggregation-induced emission effect was synthesized by grafting naphtho[2,3-c]furan-1,3-dione and 2-hydrazinylbenzo[d]thiazole. The probe N could recognize La3+ selectively and sensitively accompanied with an obvious fluorescence and color change from green to blue. Moreover, with the help of AIE properties, probe N achieved the detection of La3+ in the solid state.
Metal-organic frameworks (MOFs) are increasingly becoming an important choice for developing robust and efficient electrocatalysts; therefore, exploring the relationship between the structure, catalytic activity, and stability of MOFs is of great significance. MOFs 1-3 with different spatial configurations are designed and synthesized based on linear pyridine ligands, tetragonal carboxylic acid ligands, and triangular carboxylic acid ligands, while MOF 4 displays a three-dimensional (3D) supramolecule assembled through a mixed-ligand strategy. Compared with MOFs 1-3, MOF 4 has the lowest overpotential of 106 mV (at 10 mAcm(-2)) and a Tafel slope of 80.9 mVdec(-1), as well as sturdy long-term stability in the process of oxygen evolution reaction (OER). The presence of dense metal clusters and mu(3)-O promotes the optimal catalytic performance of MOF 4. Density functional theory (DFT) calculations of MOF 4 demonstrate that the process from O* to OOH* is the rate-determining step. This investigation further reveals the relationship between MOF structural composition and electrocatalytic OER performance and provides an effective strategy for the assembly of MOF-based electrocatalysts.
Two hypercrosslinked microporous carbazole-based polymers (namely C-POP-1 and C-POP-2) were prepared through an efficient Friedel - Crafts coupling approach. Both samples have different porous structures via regulating the length of two-node linear organic blocks. Meanwhile, they have lots of attractive advantages, such as large surface area, splendid stability and conjugate skeleton. As a research case, the aptasensor based on CPOP-2 with the large porous skeleton exhibits the excellent electrochemical detection behavior toward penicillin (PCL). More importantly, this aptasensor can quantitatively detect trace PCL in actual test samples.
Converting CO2 to valuable chemicals and fuels is a viable method to establish a carbon-neutral energy cycle in the environment. Metal-organic frameworks (MOFs), characterized by dispersed active sites, high porosity, etc., have displayed a great application prospect in the electrochemical/chemical CO2 reduction reaction (CO2RR) process. Herein, we proposed a one-step production to establish a series of pillar-layered porous MOFs, [Co-2(L)(bimb)](n) (MOF 1) and [Co-4(L)(2)(bidpe)(2)](n) (MOF 2) [H4L = 5 '-(4-carboxyphenyl)-(1,1 ':2 ',1 ''-terphenyl)-4,4 ',4 ''-tricarboxylic, bimb = 1,4-bis(imidazol-1-yl)-butane, bidpe = 4 '-bis(imidazolyl) diphenyl ether], for preferential conversion of CO2 via ligand adjustment and increase of active sites' density. According to single-crystal X-ray diffraction studies, [Co-2(L)(bimb)](n) exhibits pillar-layered binuclear 3D frameworks with a 2,4,6-linked 3-nodes new topology structure, while [Co-4(L)(2)(bidpe)(2)](n) displays pillar-layered tetranuclear interspersed networks with a 4,6-linked 2-nodes fsc topology structure through a ligand adjustment strategy. Meanwhile, the pillar-layered structure of the MOFs with abundant active sites is conducive to mass diffusion and benefits the conversion of CO2. MOFs 1-2 exhibit good electrocatalytic activity for CO2RR in 0.5 M KHCO3 solution. Especially, the current density of MOF 2 generated at -0.90 V (vs. RHE) reaches -81.6 mAcm(-2), which is 3.1 times higher than that under an Ar atmosphere. In addition, MOFs 1-2 can be used as a heterogeneous catalyst for chemical conversion of CO2. The results are expected to provide inspiration for rational design to develop stable and high-efficiency MOF-based electrocatalysts for CO2RR.
右江民族医学院于2013年开办了卫生检验与检疫本科专业,人才培养方式尚处于探索阶段,如何在大健康背景下,培养出掌握先进卫生检验技术,具备初步的卫检专业能力、应付突发公共卫生事件能力的复合型卫生检验与检疫专门人才?本研究梳理人才培养存在的问题,并从优化课程设置、多学科交叉融合发展思维开展课程建设、更新教师教育教学理念、优化教师教学方法和转变教学模式、实施过程评价和结果评价相结合、强化实践教学、做好课程思政等进行探索,为该专业高质量建设及"三得"人才培养提供参考依据.
Cobalt metal organic frameworks (Co-MOFs), as promising potential electrocatalyst materials, have been extensively investigated owing to high catalytic active center, uniform catalytic site, large specific surface area, adjustable pore. A new Co-MOF, namely, {[Co-2(L)(4,4 '-bbibp)(2)]center dot 4(H2O)}(n) [YMUN 9 (YMUN for Youjiang Medical University for Nationalities)], has been synthesized based on semi-rigid dicarboxylic acid and rigid imidazole ligands (H2L = 3,5-bis(3,5-dicarboxylphenoxy)benzoic acid, 4,4 '-bbibp = 4,4 '-bis(benzimidazol-1-yl)biphenyl). YMUN 9 displays a 3D framework through by means of single-crystal X-ray diffraction (SC-XRD). In order to present the structure more clearly, YMUN 9 can be defined as a 3D 2-nodal (4,4)-connected network with the point symbol of {4 center dot 8(5)}(2){4(2)center dot 10(4)} through topology analysis. YMUN 9-D has been obtained based on YMUN 9 through a new strategy that of programmed heat treatment of YMUN 9. The oxygen evolution reaction (OER) electrochemical activity of YMUN 9-D has been investigated through cyclic voltammetry (CV), linear scanning voltammetry (LSV), chronopotentiometry (CP), and electrochemical impedance spectroscopy (EIS), in 0.1 M KOH electrolyte. The investigated results revealing that YMUN 9-D has a prominent overpotential of 273.9 mV (at J = 10 mA center dot cm(-2)), and keeps great chemical stability until 1000 mins. The Tafel slope of YMUN 9-D is 141.9 mV center dot dec(-1) and its double layer capacitance is found to be 32 mF center dot cm(-2). Compared to other MOFs materials, YMUN 9-D displays similar or superior electrocatalytic performance.
Removal the hazards of Azo organic dyes from waterbody through porous heterogeneous materials is considered as a low-cost and high-efficient method. Intriguingly, two metal organic frameworks (MOFs), {[Co-3(L)(3)(H2O)]center dot 3.5(C4H2O2)} n and [Co-4(L)(4)(bit)(2)] (n) designated as MOF 1 and 2, have been synthesized through the traditional solvothermal method. MOF 2 exhibits significant removal effect on organic dye (congo red (CR)) from waterbody owing to more imidazole rings in the structure than 1. After optimizing the experimental conditions, the highest adsorption capacity (810.7 mg g(-1)) and high removal rate (97.28%) of 2 are obtained in 500 ppm CR solution. Pseudo second-order kinetics and Langmuir isotherms more accurately described the adsorption process of 2. In addition, 2 exhibits high recyclability, stability and adsorption performance through a simple organic solvent release system. Moreover, 2 also exhibits high adsorption performance in real wastewater. The possible mechanism of selective adsorption involves the pi-pi stacking interaction, hydrogen bond, synergistic effect of electrostatic interaction and pore filling. All the bench experiments have indicated that 2 is a promising potential sorbent in the practical wastewater treatment and CR dyes recovery.
Two Ni(II)-based monomeric complexes with the formulas of [Ni(dbb)(H2O)2] (1) and [Ni2(H2dbb)2(xda) (H2O)2] (2) (H2dbb = 6,6 '-di(benzimidazol-2-yl)-2,2 '-bipyridine, H4xda = 5,5 '-(1,4-xylylenediamino) diisoph-thalic acid) have been successfully synthesized under solvothermal conditions. Structural analysis revealed that the discrete monomers of 1 and 2 extend into high-dimensional networks through intermolecular hydrogen bonds, pi center dot center dot center dot pi stacking interactions and weak intermolecular interactions. As novel photocatalyst materials, 1 and 2 exhibited active performance towards the degradation of methyl violet (MV) under UV irradiation. Besides, the cyclic experiments indicated that 2 was stable and reusable, enabling it to be potential candidates for dye-containing wastewater treatment. The possible mechanism of the photocatalytic performance was also investi-gated in detail. Moreover, the magnetic susceptibility measurements of 1 and 2 demonstrated that week anti-ferromagnetic interactions were operative between the Ni(II) ions.
Two novel Co(II) coordination polymers (CPs), formulated as {[Co2(L)(H2O)6].H2O}n (1) and {[Co (bidpe)2(H2O)2].H2L.3.5H2O}n (2) (H4L = 3,5-bis(3,4-dicarboxylphenoxy)pyridine, bidpe = 4,4 '-bis(lmidazolyl) diphenyl ether), have been solvothermally synthesized and characterized by various techniques. Complex 1 exhibited a 2D -> 3D supramolecular framework through H-bonds with a point symbol of (12)(4.125)(4) topology. However, with the introduction of additional bibpe ligand, the H4L ligand did not coordinate with Co(II) ions in the synthesis of 2. Complex 2 possessed a 1D [Co(bidpe)2]n loop line, which was further linked by H-bonds to form a 3D supramolecular architecture. In particular, both the CPs exhibited efficient photocatalytic activities towards the degradation of methyl violet (MV) under low-energy irradiation of a 125 W Hg lamp, which could be attributed to their high efficiencies in generating .OH radicals. Moreover, the variable-temperature magnetic analyses indicated that 1 and 2 exhibit antiferromagnetic behavior between the adjacent Co(II) ions.
培养具有科研能力和创新能力的高素质人才,是当前各高校教育工作的核心内容之一,也是我国到2035年基本实现中国特色社会主义现代化和2050年全面建成社会主义现代化强国的重要保证之一.以右江民族医学院医学检验学院为例,开展科教融合主导大学生科研创新能力培养模式的实践活动.结果表明,基于科教融合主导大学生科研创新能力的培养模式可以有效提升大学生的科研和创新能力.
In this work, a pair of chiral coordination compounds with formula as Cd[D-OH-bim](2)(NO3)(2) (1-D) and Cd[L-OH-bim]2(NO3)(2) (1-L) (L-OH-bim = (L)-2-(1-Hydroxyethyl)benzimidazole; D-OH-bim = (D)-2-(1-Hydroxyethyl) benzimidazole) are synthesized for circular polarization luminescence (CPL). Single crystal X-ray diffraction (SCXRD) results show that the 1-D and 1-L contain chiral Cd[OH-bim]2(NO3)(2) units composed of Cd center and chiral OH-bim ligand (D-or L-OH-bim) as well as NO3-. The self-assembly of these chiral units by hydrogen bonding interaction generates a 3D hydrogen-bonded framework containing multiple chirality, such as chiral ligand, helical chain, chiral spatial arrangement and chiral framework (chiral space group and chiral topology). The bulk phase with multilevel chirality shows enhanced circular dichroism response and obvious CPL than that of the organic ligands as well as Cd[OH-bim](2)(NO3)(2 )unit.