Exploring the Role of Amino Acid-Derived Multivariate Metal-Organic Frameworks as Catalysts in Hemiketalization Reactions.

Understanding the host-guest chemistry in MOFs represents a research field with outstanding potential to develop in a rational manner novel porous materials with improved performances in fields such as heterogeneous catalysis. Herein, we report a family of three isoreticular MOFs derived from amino acids and study the influence of the number and nature of functional groups decorating the channels as a catalyst in hemiketalization reactions. In particular, a multivariate (MTV) MOF 3, prepared by using equal percentages of amino acids L-serine and L-mecysteine, in comparison to single-component ("traditional") MOFs, derived from either L-serine or L-mecysteine (MOFs 1 and 2), exhibits the most efficient catalytic conversions for the hemiketalization of different aldehydes and ketalization of cyclohexanone. On the basis of the experimental data reported, the good catalytic performance of MTV-MOF 3 is attributed to the intrinsic heterogeneity of MTV-MOFs. These results highlight the potential of MTV-MOFs as strong candidates to mimic natural nonacidic enzymes, such as glycosidases, and to unveil novel catalytic mechanisms not so easily accessible with other microporous materials.

(Multivariate)-Metal-Organic Framework for Highly Efficient Antibiotic Capture from Aquatic Environmental Matrices.

Contamination of aquatic environments by pharmaceuticals used by modern societies has become a serious threat to human beings. Among them, antibiotics are of particular concern due to the risk of creating drug-resistant bacteria and, thus, developing efficient protocols for the capture of this particular type of drug is mandatory. Herein, we report a family of three isoreticular MOFs, derived from natural amino acids, that exhibit high efficiency in the removal of a mixture of four distinct families of antibiotics, such as fluoroquinolones, penicillins, lincomycins, and cephalosporins, as solid-phase extraction (SPE) sorbents. In particular, a multivariate (MTV)-MOF, prepared using equal percentages of amino acids l-serine and l-methionine, also exhibits outstanding recyclability, surpassing the benchmark material activated carbon. The good removal performance of the MTV-MOF was rationalized by means of single-crystal X-ray diffraction. These results highlight the situation of MOFs as a real and promising alternative for the capture of antibiotics from environmental matrices, especially wastewater streams.

Multivariate Metal-Organic Framework/Single-Walled Carbon Nanotube Buckypaper for Selective Lead Decontamination.

The search for efficient technologies empowering the selective capture of environmentally harmful heavy metals from wastewater treatment plants, at affordable prices, attracts wide interest but constitutes an important technological challenge. We report here an eco-friendly single-walled carbon nanotube buckypaper (SWCNT-BP) enriched with a multivariate amino acid-based metal-organic framework (MTV-MOF) for the efficient and selective removal of Pb2+ in multicomponent water systems. Pristine MTV-MOF was easily immobilized within the porous network of entangled SWCNTs, thus obtaining a stable self-standing adsorbing membrane filter (MTV-MOF/SWCNT-BP). SWCNT-BP alone shows a moderately good removal performance with a maximum adsorption capacity of 180 mg·g-1 and a considerable selectivity for Pb(II) ions in highly concentrated multi-ion solutions over a wide range of lead concentration (from 200 to 10000 ppb). Remarkably, these features were outperformed with the hybrid membrane filter MTV-MOF/SWCNT-BP, exhibiting enhanced selectivity and adsorption capacity (310 mg·g-1, which is up to 42% higher than that of the neat SWCNT-BP) and consequently enabling a more efficient and selective removal of Pb2+ from aqueous media. MTV-MOF/SWCNT-BP was able to reduce [Pb2+] from the dangerous 1000 ppb level to acceptable limits for drinking water, below 10 ppb, as established by the current EPA and WHO limits. Thus, the eco-friendly composite MTV-MOF/SWCNT-BP shows the potential to be effectively used several times as a reliable adsorbent for Pb2+ removal for household drinking water or in industrial treatment plants for water and wastewater lead decontamination.

Epoxidation vs. dehydrogenation of allylic alcohols: heterogenization of the VO(acac)2 catalyst in a metal-organic framework.

Allylic alcohol epoxidation and dehydrogenation reactivity is distinguished when VO(acac)2 is used in solution or anchored in a metal-organic framework (MOF). The chemical mechanism depends on the electronic profile of alkene substituents when the vanadyl complex is used in the homogenous phase. However, confinement effects imparted by MOF channels allow gaining control of the chemoselectivity toward the dehydrogenation product.

Metal-Organic Frameworks as Unique Platforms to Gain Insight of σ-Hole Interactions for the Removal of Organic Dyes from Aquatic Ecosystems.

The combination of high crystallinity and rich host-guest chemistry in metal-organic frameworks (MOFs), have situated them in an advantageous position, with respect to traditional porous materials, to gain insight on specific weak noncovalent supramolecular interactions. In particular, sulfur σ-hole interactions are known to play a key role in the biological activity of living beings as well as on relevant molecular recognitions processes. However, so far, they have been barely explored. Here, we describe both how the combination of the intrinsic features of MOFs, especially the possibility of using single-crystal X-ray crystallography (SCXRD), can be an extremely valuable tool to gain insight on sulfur σ-hole interactions, and how their rational exploitation can be enormously useful in the efficient removal of harmful organic molecules from aquatic ecosystems. Thus, we have used a MOF, prepared from the amino acid L-methionine and possessing channels decorated with -CH2 CH2 SCH3 thioalkyl chains, to remove a family of organic dyes at very low concentrations (10 ppm) from water. This MOF is able to efficiently capture the four dyes in a very fast manner, reaching within five minutes nearly the maximum removal. Remarkably, the crystal structure of the different organic dyes within MOFs channels could be determined by SCXRD. This has enabled us to directly visualize the important role sulfur σ-hole interactions play on the removal of organic dyes from aqueous solutions, representing one of the first studies on the rational exploitation of σ-hole interactions for water remediation.

Highly Efficient Removal of Neonicotinoid Insecticides by Thioether-Based (Multivariate) Metal-Organic Frameworks.

Circumventing the impact of agrochemicals on aquatic environments has become a necessity for health and ecological reasons. Herein, we report the use of a family of five eco-friendly water-stable isoreticular metal-organic frameworks (MOFs), prepared from amino acids, as adsorbents for the removal of neonicotinoid insecticides (thiamethoxam, clothianidin, imidacloprid, acetamiprid, and thiacloprid) from water. Among them, the three MOFs containing thioether-based residues show remarkable removal efficiency. In particular, the novel multivariate MOF {SrIICuII6[(S,S)-methox]1.5[(S,S)-Mecysmox]1.50(OH)2(H2O)}·36H2O (5), featuring narrow functional channels decorated with both -CH2SCH3 and -CH2CH2SCH3 thioalkyl chains-from l-methionine and l-methylcysteine amino acid-derived ligands, respectively-stands out and exhibits the higher removal efficiency, being capable to capture 100% of acetamiprid and thiacloprid in a single capture step under dynamic solid-phase extraction conditions-less than 30 s. Such unusual combination of outstanding efficiency, high stability in environmental conditions, and low-cost straightforward synthesis in 5 places this material among the most attractive adsorbents reported for the removal of this type of contaminants.

Publisher Correction: Hydrolase-like catalysis and structural resolution of natural products by a metal-organic framework.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Hydrolase-like catalysis and structural resolution of natural products by a metal-organic framework.

The exact chemical structure of non-crystallising natural products is still one of the main challenges in Natural Sciences. Despite tremendous advances in total synthesis, the absolute structural determination of a myriad of natural products with very sensitive chemical functionalities remains undone. Here, we show that a metal-organic framework (MOF) with alcohol-containing arms and adsorbed water, enables selective hydrolysis of glycosyl bonds, supramolecular order with the so-formed chiral fragments and absolute determination of the organic structure by single-crystal X-ray crystallography in a single operation. This combined strategy based on a biomimetic, cheap, robust and multigram available solid catalyst opens the door to determine the absolute configuration of ketal compounds regardless degradation sensitiveness, and also to design extremely-mild metal-free solid-catalysed processes without formal acid protons.