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Antibiotics are found in natural waters, raising concern about their human and environmental toxicity and the wide occurrence of antibiotic resistant bacteria. The antibiotic resistance crisis is attributed to the overuse and misuse of these medications. Particularly, sulfamethazine (SMT), an antibiotic commonly used in pigs and cattle for the treatment of bacterial diseases, has been detected in the natural environment (soil and water). Among all the technologies developed to combat the deteriorating water quality and control antimicrobial resistance, heterogeneous photocatalysis should be highlighted for the degradation of refractory organic compounds. Here, we described the SMT adsorption and photodegradation capacity of a highly porous and robust zirconium-based MOF UiO-66 under realistic conditions, and its potential recyclability. Further, its SMT removal capacity was improved by functionalizing the MOF porosity (28.5% of SMT adsorption in 24 h for nanoUiO-66-NH 2 ), and nanosizing the MOF (100% SMT photodegradation in only 4 h for nanoUiO-66). Finally, the safety of the formed by-product during SMT photodegradation was confirmed, reinforcing the potential of the application of UiO-66 in water remediation.

Proton-exchange membrane fuel cells are an attractive green technology for energy production. However, one of their major drawbacks is instability of the electrolytes under working conditions (i.e., temperature and humidity). Some metal-organic frameworks (MOFs) have recently emerged as promising alternative electrolyte materials because of their higher stability (compared with the organic polymers currently used as electrolytes), proton conductivity, and outstanding porosity and versatility. Here, we present ionic exchange in a microporous zirconium phosphonate, UPG-1, as an efficient strategy to enhance its conductivity and cyclability. Thus, labile protons of the hybrid structure were successfully replaced by different alkali cations (Li + , Na + , and K + ), leading to 2 orders of magnitude higher proton conductivity than the pristine UPG-1 (up to 2.3 × 10 -2 S·cm -1 , which is comparable with those of the commercial electrolytes). Further, the proton conductivity was strongly influenced by the MOF hydrophilicity and the polarization strength of the cation, as suggested by molecular simulation. Finally, a mixed-matrix membrane containing the best-performing material (the potassium-exchanged one) was successfully prepared, showing moderate proton conductivity (up to 8.51 × 10 -3 S·cm -1 ).

Despite the interesting chemopreventive, antioxidant and antiangiogenic effects of the natural bioflavonoid genistein (GEN), its low aqueous solubility and bioavailability make it necessary to administer it using a suitable drug carrier system. Nanometric porous metal-organic frameworks (nanoMOFs) are appealing systems for drug delivery. Particularly, mesoporous MIL-100(Fe) possesses a variety of interesting features related to its composition and structure, which make it an excellent candidate to be used as a drug nanocarrier (highly porous, biocompatible, can be synthesized as homogenous and stable nanoparticles (NPs), etc.). In this study, GEN was entrapped via simple impregnation in MIL-100 NPs achieving remarkable drug loading (27.1 wt%). A combination of experimental and computing techniques was used to achieve a deep understanding of the encapsulation of GEN in MIL-100 nanoMOF. Subsequently, GEN delivery studies were carried out under simulated physiological conditions, showing on the whole a sustained GEN release for 3 days. Initial pharmacokinetic and biodistribution studies were also carried out upon the oral administration of the GEN@MIL-100 NPs in a mouse model, evidencing a higher bioavailability and showing that this oral nanoformulation appears to be very promising. To the best of our knowledge, the GEN-loaded MIL-100 will be the first antitumor oral formulation based on nanoMOFs studied in vivo, and paves the way to the efficient delivery of nontoxic antitumorals via a convenient oral route.

Combined therapies emerge as an interesting tool to overcome limitations of traditional pharmacological treatments (efficiency, side effects). Among other materials, metal-organic frameworks (MOFs) offer versatilities for the accommodation of multiple and complementary active pharmaceutical ingredients (APIs): accessible large porosity, availability of functionalization sites, and biocompatibility. Here, we propose topical patches based on water-stable and biosafe Fe carboxylate MOFs (MIL-100 and MIL-127), the biopolymer polyvinyl alcohol (PVA) and two co-encapsulated drugs used in skin disorders (azelaic acid (AzA) as antibiotic, and nicotinamide (Nic) as anti-inflammatory), in order to develop an advanced cutaneous combined therapy. Exceptional MOF drug contents were reached (total amount 77.4 and 48.1 wt.% for MIL-100 and MIL-127, respectively), while an almost complete release of both drugs was achieved after 24 h, adapted to cutaneous delivery. The prepared cutaneous PVA-MOF formulations are safe and maintain the high drug-loading capacity (total drug content of 38.8 and 24.2 wt.% for MIL-100 and MIL-127, respectively), while allowing a controlled delivery of their cargoes, permeating through the skin to the active target sites. The total amount of drug retained or diffused through the skin is within the range (Nic), or even better (AzA) than commercial formulations. The presented results make these drug combined formulations promising candidates for new cutaneous devices for skin treatment.

The first bioinspired microporous metal-organic framework (MOF) synthesized using ellagic acid, a common natural antioxidant and polyphenol building unit, is presented. Bi 2 O(H 2 O) 2 (C 14 H 2 O 8 )· n H 2 O (SU-101) was inspired by bismuth phenolate metallodrugs, and could be synthesized entirely from nonhazardous or edible reagents under ambient aqueous conditions, enabling simple scale-up. Reagent-grade and affordable dietary supplement-grade ellagic acid was sourced from tree bark and pomegranate hulls, respectively. Biocompatibility and colloidal stability were confirmed by in vitro assays. The material exhibits remarkable chemical stability for a bioinspired MOF (pH = 2-14, hydrothermal conditions, heated organic solvents, biological media, SO 2 and H 2 S), attributed to the strongly chelating phenolates. A total H 2 S uptake of 15.95 mmol g -1 was recorded, representing one of the highest H 2 S capacities for a MOF, where polysulfides are formed inside the pores of the material. Phenolic phytochemicals remain largely unexplored as linkers for MOF synthesis, opening new avenues to design stable, eco-friendly, scalable, and low-cost MOFs for diverse applications, including drug delivery.

Water is essential in all aspects of life, being the defining characteristic of our planet and even our body. Regrettably, water pollution is increasingly becoming a challenge due to novel anthropogenic pollutants. Of particular concern are emerging organic contaminants (EOCs), the term used not only to cover newly developed compounds but also compounds newly discovered as contaminants in the environment. Aside from anthropogenic contamination, higher temperature and more extreme and less predictable weather conditions are projected to affect water availability and distribution. Therefore, wastewater treatment has to become a valuable water resource and its reuse is an important issue that must be carried out efficiently. Among the novel technologies considered in water remediation processes, metal-organic frameworks (MOFs) are regarded as promising materials for the elimination of EOCs since they present many properties that commend them in water treatment: large surface area, easy functionalizable cavities, some are stable in water, and synthesized at large scale, etc. This review highlights the advances in the use of MOFs in the elimination (adsorption and/or degradation) of EOCs from water, classifying them by the nature of the contaminant.

Glycosaminoglycans (GAGs) are biomacromolecules necessary for the regulation of different biological functions. In medicine, GAGs are important commercial therapeutics widely used for the treatment of thrombosis, inflammation, osteoarthritis and wound healing. However, protocols for the encapsulation of GAGs in MOFs carriers are not yet available. Here, we successfully encapsulated GAG-based clinical drugs (heparin, hyaluronic acid, chondroitin sulfate, dermatan sulfate) and two new biotherapeutics in preclinical stage (GM-1111 and HepSYL proteoglycan) in three different pH-responsive metal-azolate frameworks (ZIF-8, ZIF-90, and MAF-7). The resultant GAG@MOF biocomposites present significant differences in terms of crystallinity, particle size, and spatial distribution of the cargo, which influences the drug-release kinetics upon applying an acidic stimulus. For a selected system, heparin@MOF, the released therapeutic retained its antithrombotic activity while the MOF shell effectively protects the drug from heparin lyase. By using different MOF shells, the present approach enables the preparation of GAG-based biocomposites with tunable properties such as encapsulation efficiency, protection and release., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Although nanoscaled metal-organic frameworks (nanoMOFs) are promising drug carriers, their appropriate formulation remains almost unexplored and basically restricted to intravenous routes. Lungs, beneficiating from a large absorption surface and low enzymatic presence, are a very attractive target for both local and systemic delivery. However, pulmonary nanoMOF formulation is a pending and defying task. Thus, we propose a pioneer nanoMOF-based microsphere system as a potential platform for pulmonary administration. A biocompatible nanoMOF was successfully encapsulated in mannitol by a simple and continuous spray-drying technique. Upon intratracheal administration to rats, the resulting formulation, exhibiting optimal properties ( i.e ., homogeneity, size, density, and spray-drying process yield), was able to release the intact nanoMOF carrier uniformly along the lungs, reaching the bronchioles and alveoli.

Inorganic semiconductors are extensively considered to be among the most promising materials to convert solar light into electricity or chemical energy owing to their efficiency in the separation of photoinduced electron/hole. Bismuth oxides, and, in particular, those built up of [Bi 2 O 2 ] 2+ layers, show an efficient charge separation and, thus, high photocatalytic activities. To explore a possible synergetic effect of bismuth metallic nodes combined with the electron-rich linker squarate, Bi 2 O 2 (C 4 O 4 ) or IEF-3 (an IMDEA Energy framework) was hydrothermally prepared and adequately characterized. As determined from the X-ray structure, [Bi 2 O 2 ] 2+ layers are interconnected by squarate ligands, having a pronounced effect of the 6s 2 lone pair on the bismuth local environment. IEF-3 shows high thermal and chemical robustness at industrially relevant model aggressive media. A large panel of physicochemical methods were applied to recognize IEF-3 as an UV-absorbing n-type semiconductor, showing a photocurrent response comparable to that of α-Bi 2 O 3 , offering further possibilities for tuning its electrochemical properties by modifying the ligand. In this way, the well-known compositional and structural versatility of coordination polymers may be applied in the future to fine-tune metal-organic semiconductor systems.

The structural behaviour under mechanical stimuli of two metal organic frameworks, UiO-66(Zr) and MIL-125(Ti) and their amino-functionalized derivatives has been investigated by high-pressure powder X-ray diffraction up to 3.5 GPa. All these solids showed a gradual pressure-induced reversible decrease of their crystallinity and UiO-66(Zr)_NH2 material has been revealed as one of the most resilient MOFs reported so far corresponding to a very high bulk modulus. The mechanical behaviors of these MOFs have been correlated to their chemical and geometric features including the metal-oxygen coordination number, the nature of the organic linker, the porosity as well as their crystal density.

The influence of the constitutive dicarboxylate linkers (size, functional group) over the crystallization kinetics of a series of porous Zr metal-organic frameworks with the UiO-66 topology has been investigated by in situ time-resolved energy dispersive X-ray diffraction (EDXRD). Both large aromatic spacers (2,6-naphthalene-, 4,4'-biphenyl- and 3,3'-dichloro-4,4'-azobenzene-dicarboxylates) and a series of X-functionalized terephthalates (X=NH2 , NO2 , Br, CH3 ) were investigated in dimethylformamide (DMF) at different temperatures and compared with the parent UiO-66. Using different crystallization models, rate constants and further kinetic parameters (such as activation energy) have been extracted. Finally, the impact of the replacement of the toxic DMF by water on the crystallization kinetics was studied through the synthesis of the functionalized UiO-66-NO2 solid., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The class of highly porous materials called metal-organic frameworks offer many opportunities for applications across biology and medicine. Their wide range of chemical composition makes toxicologically acceptable formulation possible, and their high level of functionality enables possible applications as imaging agents and as delivery vehicles for therapeutic agents. The challenges in the area encompass not only the development of new solids but also improvements in the formulation and processing of the materials, including tailoring the morphology and surface chemistry of the frameworks to fit the proposed applications.

The efficient delivery of drugs in the body requires the use of non-toxic nanocarriers. Most of the existing materials show poor drug loading and/or rapid release of the proportion of the drug that is simply adsorbed (or anchored) at the external surface of the nanocarrier. The new porous hybrid solids, with the ability to tune their structures and porosities are well suited to serve as nanocarriers for delivery and imaging applications. Here we show that specific non-toxic porous iron(III) - based metal - organic frameworks with engineered cores and surfaces, as well as imaging properties, function as superior nanocarriers for efficient controlled delivery of antitumour and retroviral drugs against cancer and AIDS. They also potentially associate therapeutics and diagnostics, and open the way for theranostics, or -personalized patient treatments. double dagger.