Amyloid detection in neurodegenerative diseases using MOFs.

Neurodegenerative diseases (amyloid diseases such as Alzheimer's and Parkinson's), stemming from protein misfolding and aggregation, encompass a spectrum of disorders with severe systemic implications. Timely detection is pivotal in managing these diseases owing to their significant impact on organ function and high mortality rates. The diverse array of amyloid disorders, spanning localized and systemic manifestations, underscores the complexity of these conditions and highlights the need for advanced detection methods. Traditional approaches have focused on identifying biomarkers using imaging techniques (PET and MRI) or invasive procedures. However, recent efforts have focused on the use of metal-organic frameworks (MOFs), a versatile class of materials known for their unique properties, in revolutionizing amyloid disease detection. The high porosity, customizable structures, and biocompatibility of MOFs enable their integration with biomolecules, laying the groundwork for highly sensitive and specific biosensors. These sensors have been employed using electrochemical and photophysical techniques that target amyloid species under neurodegenerative conditions. The adaptability of MOFs allows for the precise detection and quantification of amyloid proteins, offering potential advancements in early diagnosis and disease management. This review article delves into how MOFs contribute to detecting amyloid diseases by categorizing their uses based on different sensing methods, such as electrochemical (EC), electrochemiluminescence (ECL), fluorescence, Förster resonance energy transfer (FRET), up-conversion luminescence resonance energy transfer (ULRET), and photoelectrochemical (PEC) sensing. The drawbacks of MOF biosensors and the challenges encountered in the field are also briefly explored from our perspective.

Efficient Dye Extraction from Wastewater Using Indium-MOF-Immobilized Polyvinylidene Fluoride Membranes with Selective Filtration for Enhanced Remediation.

Industrial activities have led to releasing harmful substances into the environment, necessitating the elimination of these toxic compounds from wastewater. Organic dyes, commonly found in industrial effluents, pose a threat to ecosystems and human health. Conventional treatment methods often suffer from limitations such as high cost and poor efficiency. Metal-organic frameworks (MOFs) have emerged as promising materials for selective separation, including membrane filtration (MF). Mixed-matrix membranes (MMMs) combining MOFs with polymers offer improved filtration properties. In this study, MMMs were fabricated by incorporating synthesized In-MOF with a polyvinylidene fluoride (PVDF) polymer (In-MOF@PVDF MMMs) using the nonsolvent-induced phase separation process. The MMMs were evaluated for the MF of various organic dyes, achieving notable removal efficiencies. The membrane containing 20% In-MOF (M4) demonstrated exceptional performance, removing 99% of the methylene blue (MB) dye. Additionally, membrane M4 effectively filtered Azure A (AZA), Azure B (AZB), and toluidine blue O (TOLO) with a removal efficiency of 99%. However, for Rhodamine B (RHB) and methyl orange (MO), the removal efficiencies were slightly lower at 74 and 39%, respectively. Further, these membranes are utilized in selective dye filtration in the MB+/RHB+ and MB+/MO- systems, where the selectivity was found for MB. The isothermal and DFT studies revealed the membrane's behavior with dye mixtures, while water stability and regeneration studies confirmed its durability. Thus, these findings highlight the potential of In-MOF@PVDF MMMs for effective and selective dye removal in wastewater treatment applications.

Covalent Organic Framework Impregnated with Silver and Copper Nanoparticles: An Advanced Approach for Catalytic Degradation of Organic Pollutants in Wastewater.

In this study, we introduce an economically viable and scalable process for developing a novel covalent organic framework (COF), which is a cross-linked polymer. The resulting material, TzTFB-COF, is successfully functionalized with silver and copper nanoparticles, which show high adequacy in the degradation of nitroaromatic compounds (NACs). For the synthesis of TzTFB-COF, s-tetrazine diamine (Tz) and 1,3,5-triformylbenzene (TFB) are chosen as building blocks, which exhibit a high density of nitrogen-containing sites. TzTFB-COF shows good chemical and thermal stability (>300 °C). For functionalization of TzTFB-COF with silver and copper nanoparticles, a solution infiltration technique is used. The composite materials, i.e., Ag@TzTFB-COF and Cu@TzTFB-COF, have been characterized using various spectroscopic and analytical techniques, which show high activity, high selectivity, and excellent chemical and thermal stability up to 350 °C. The silver and copper contents of Ag@TzTFB-COF and Cu@TzTFB-COF are determined to be 9.6 and 12.4 wt % by inductively coupled plasma optical emission spectrometer (ICP-OES). The catalytic efficiency of the synthesized Ag@TzTFB-COF and Cu@TzTFB-COF materials is assessed in the context of catalyzing the hydrogenation of NACs. Experimental results reveal a remarkable catalytic performance when conducted in an aqueous medium, and notably, the materials demonstrate substantial potential for reusability across multiple catalytic cycles. The determined parameters for the catalytic hydrogenation reaction, i.e., the rate constants and Gibbs free energies, are found to be 0.0185 s-1 and 9.878 kJ/mol for Ag@TzTFB-COF and 0.0219 s-1 and 9.615 kJ/mol for Cu@TzTFB-COF. Thus, the catalytic reaction exhibits characteristics of endothermic, endergonic, and nonspontaneous nature.

Improving Copper(II) Sensitivity by Combined use of AIEE Active and Inactive Schiff Bases.

An aggregation-induced emission enhancement (AIEE) active Schiff base PNN was synthesized by condensing benzidine with 2-hydroxynaphthaldehyde. The green-fluorescent PNN (λem = 510 nm) in DMF turned to yellow-fluorescent PNN (λem = 557 nm) upon increasing the fractions of HEPES buffer (10 mM, pH 7.4) above 40%. The DLS study supports the self-aggregation of PNN that restricts the intramolecular rotation and activates the excited-state intramolecular proton transfer (ESIPT) process. The fluorescence emission of AIEE active PNN was quenched by Cu2+ with an estimated detection limit of 2.1 µM. Interestingly, the detection limit of PNN towards Cu2+ was improved in the presence of an AIEE inactive Schiff base PBPM obtained by reacting 1,4-diaminobenzene with pyridine-4-carbaldehyde. The mixed PNN-PBPM showed a detection limit of 0.49 µM. The practical utility of PNN-PBPM was validated by quantifying Cu2+ ions in real environmental water samples and green tea.

MOF/POM hybrids as catalysts for organic transformations.

Insertion of molecular metal oxides, e.g. polyoxometalates (POMs), into metal-organic frameworks (MOFs) opens up new research opportunities in various fields, particularly in catalysis. POM/MOF composites have strong acidity, oxygen-rich surface, and redox capacity due to typical characteristics of POMs and the large surface area, highly organized structures, tunable pore size, and shape are due to MOFs. Such hybrid materials have gained a lot of attention due to astonishing structural features, and hence have potential applications in organic catalysis, sorption and separation, proton conduction, magnetism, lithium-ion batteries, supercapacitors, electrochemistry, medicine, bio-fuel, and so on. The exceptional chemical and physical characteristics of POMOFs make them useful as catalysts in simple organic transformations with high capacity and selectivity. Here, the thorough catalytic study starts with a brief introduction related to POMs and MOFs, and is followed by the synthetic strategies and applications of these materials in several catalytic organic transformations. Furthermore, catalytic conversions like oxidation, condensation, esterification, and some other types of catalytic reactions including photocatalytic reactions are discussed in length with their plausible catalytic mechanisms. The disadvantages of the POMOFs and difficulties faced in the field have also been explored briefly from our perspectives.

Insights into organic-inorganic hybrid molecular materials: organoimido functionalized polyoxomolybdates.

Polyoxometalates (POMs) are polyatomic anions that comprise transition metal group 5 (V, Nb, Ta) or group 6 (Mo, W) oxyanions connected together by shared oxygen atoms. POMs are fascinating because of their exclusive and remarkable characteristics. One of the most interesting features of POMs is their capability to function as an electron relay by performing stepwise multi-electron redox reactions while maintaining their structural integrity. Functionalization of POMs with amino organic compounds results in organoimido derivatives of polyoxometalates, which have aroused interest due to augmentation of their properties. Comprehensive study has shown that the synthesis methodologies to obtain desired organoimido derivatives of POMs by employing various imido-releasing reagents have progressed drastically in recent decades, particularly the innovative DCC-dehydrating technique. These organoimido functionalized POMs have been used as major building blocks to develop unique nanostructured organic-inorganic hybrid molecular materials. Many conventional organic synthesis processes such as Pd-catalyzed carbon-carbon coupling and esterification reactions have been performed with organoimido functionalized POMs where the presence of POM triggered the reaction process. Thus, investigation of the reactivity of organoimido derivatives of POMs foreshadows the intriguing future of POMs chemistry.

A [4+2] Condensation Strategy to Imine-Linked Single-Crystalline Zeolite-Like Zinc Phosphate Frameworks.

Double-4-ring zinc phosphate (D4R), [Zn(dipp)(4-Py-CHO)]4 (2) (dipp=diiminopyridine), bearing four formyl groups, has been utilized as a building block (SBU) for the synthesis of a new class of imine-linked [4+2] COF-like polycrystalline zinc phosphate frameworks. Reactions of 2 with a series of linear aromatic diamines results in the formation of polycrystalline frameworks [Zn4 (dipp)4 (L)2 ]n (3-6) (L=L1 to L4 , diimines formed by condensation of 4-pyridine carboxaldehyde with diamines). Employing an alternative synthetic strategy, through a diffusion-controlled slow reaction of 2 with the pre-synthesized 4,4'-bispyridyl bisimine (L3 ), [Zn4 (dipp)4 (L3 )2 ]n (5') has been obtained as single crystals. Complex 5' is a 3D-framework, exhibiting a rare eightfold interpenetrated diamondoid network. The long spacer length (19.6 Å) results in extensive entanglement in 5'. Powder diffraction data suggest that these compounds are isoreticular 3D-frameworks. To study the effect of the relative position of pyridyl donors with respect to the central benzidine moiety, 3,3'-bispyridyl bisimine (L5 ) was investigated as the spacer. A slow reaction of 1 b with L5 leads to the isolation of a 2D-boxed-sheet coordination polymer [Zn4 (dipp)4 (L5 )2 ]n (7). Selective formation of 3D-framework 5' from L3 and the 2D-framework 7 from L5 is due to the angles created by the coordination of para- and meta-pyridyl nitrogen centers at the zinc centers of the D4R cubane. Compound 5' has been utilized as a catalyst for Knoevenagel condensation.

Ab initio chemical synthesis of designer metal phosphate frameworks at ambient conditions.

Stepwise hierarchical and rational synthesis of porous zinc phosphate frameworks by predictable and directed assembly of easily isolable tetrameric zinc phosphate [Zn(dipp)(solv)]4 (dippH2 = diisopropylphenyldihydrogen phosphate; solv = CH3OH or dimethyl sulfoxide) with D4R (double-4-ring) topology has been achieved. The preformed and highly robust D4R secondary building unit can be coordinatively interconnected through a varied choice of bipyridine-based ditopic spacers L1-L7 to isolate eight functional zinc phosphate frameworks, [Zn4(dipp)4(L1)1.5(DMSO)]·4H2O (2), [Zn4(dipp)4(L2)1.5(CH3OH)] (3), [Zn4(dipp)4(L1)2] (4), [Zn4(dipp)4(L3)2] (5), [Zn4(dipp)4(L4)2] (6), [Zn4(dipp)4(L5)2] (7), [Zn4(dipp)4(L6)2] (8), and [Zn4(dipp)4(L7)2] (9), in good yield. The preparative procedures are simple and do not require high pressure or temperature. Surface area measurements of these framework solids show that the guest accessibility of the frameworks can be tuned by suitable modification of bipyridine spacers.