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Four different metal–organic framework powders (UiO-66, UiO-66-NH2, UiO-67, and HKUST-1) were shaped into tablets. The effect of the applied pressure on porous properties, mechanical resistance and tablet bulk density is reported. We observe a linear relationship between densification and tensile strength for all four studied MOFs, with the slope being MOF-dependent. We also report conditions for improving significantly the volumetric uptake. Finally, we evaluated our tablets' stability over time in the presence of moisture. [ABSTRACT FROM AUTHOR]

This article provides a comprehensive review of the nature of catalytic sites in MOFs. In the last decade, a number of striking studies have reported outstanding catalytic activities of MOFs. In all cases, the authors were intrigued as it was unexpected from the ideal structure. We demonstrate here that (surface) defects are at the origin of the catalytic activities for the reported examples. The vacancy of ligands or linkers systematically generates (surface) terminations which can possibly show Lewis and/or Brønsted acido-basic features. The engineering of catalytic sites at the nodes by the creation of defects (on purpose) appears today as a rational approach for the design of active MOFs. Similarly to zeolite post-treatments, post-modifications of MOFs by linker or metal cation exchange appear to be methods of choice. Despite the mild acidity of defective MOFs, we can account for very active MOFs in a number of catalytic applications which show higher performances than zeolites or benchmark catalysts. [ABSTRACT FROM AUTHOR]

Fourteen patients with normal preoperative renal function underwent aortocoronary bypass graft using cardiopulmonary bypass (CPB) with pulsatile (P; n = 7) or non pulsatile (NP; n = 7) perfusion. In the two groups prebypass values of plasma renin activity (PRA) and urine β-microglobulin (β-M) were within normal limits. PRA increased significantly during CPB and the first 6 h after CPB only in the non-pulsatile group. In both groups, the urine β-M level increased significantly during and after CPB; however, there was no significant difference in urine β-M levels between the two groups. Also, the amount of β-M excreted in urines per unit of time increased significantly in both groups during and after CPB; there was no significant difference between the two groups. [ABSTRACT FROM PUBLISHER]

The article discusses cutaneous porphyria in adults. Since 1951 authors have been able to make quite a thorough study of seventeen cases of a bullous affection of the skin which fits in with the porphyria group. The age of patients at the onset of their illness was between 39 and 66 with a marked predominance in the male. Histologically, cutaneous porphyria appears quite characteristic. Authors biopsies, which have all been carried out on bullae from the palms and fingers, have revealed changes so similar that it is possible to pick out a number of common features.

We report a patient with multiple myeloma who suffered from hyperammonemia after a second stem cell autograft. This syndrome is not well known but is associated with a high mortality rate. Considering the possibility of this diagnosis in patients developing confusion and neurological degradation with respiratory alkalosis after intensive chemotherapy, could allow earlier treatment and perhaps improved survival. Possible mechanisms and potential therapies are discussed. With rapid recognition and treatment of the syndrome, the patient fully recovered. One and a half years later, she is still alive and well, on interferon for persisting myeloma. Bone Marrow Transplantation (2000) 26, 343–345. [ABSTRACT FROM AUTHOR]

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Catalysis plays a crucial role in advancing sustainability. The unique reactivity of frustrated Lewis pairs (FLPs) is driving an ever-growing interest in the transition metal-free transformation of small molecules like CO 2 into valuable products. In this area, there is a recent growing incentive to heterogenize molecular FLPs into porous solids, merging the benefits of homogeneous and heterogeneous catalysis - high activity, selectivity, and recyclability. Despite the progress, challenges remain in preventing deactivation, poisoning, and simplifying catalyst-product separation. This review explores the expanding field of FLPs in catalysis, covering existing molecular FLPs for CO 2 hydrogenation and recent efforts to design heterogeneous porous systems from both experimental and theoretical perspectives. Section 2 discusses experimental examples of CO 2 hydrogenation by molecular FLPs, starting with stoichiometric reactions and advancing to catalytic ones. It then examines attempts to immobilize FLPs in porous matrices, including siliceous solids, metal-organic frameworks (MOFs), covalent organic frameworks, and disordered polymers, highlighting current limitations and challenges. Section 3 then reviews computational studies on the mechanistic details of CO 2 hydrogenation, focusing on H 2 splitting and hydride/proton transfer steps, summarizing efforts to establish structure-activity relationships. It also covers the computational aspects on grafting FLPs inside MOFs. Finally, Section 4 summarizes the main design principles established so far, while addressing the complexities of translating computational approaches into the experimental realm, particularly in heterogeneous systems. This section underscores the need to strengthen the dialogue between theoretical and experimental approaches in this field.

PSII-inspired quantasomes have emerged as promising artificial photosystems evolving oxygen from water due to their integrated multi-chromophore asset, hierarchical architecture, and efficient light-harvesting capabilities. In this study, we adopt a combined covalent and supramolecular strategy by implementing a poly-styrene backbone that reinforces proximity and pairing between adjacent perylenebisimide (PBI) quantasome units. The covalent fixation of the quantasome network results in a significant enhancement of the photoelectrocatalytic performance on engineered IO-ITO photoanodes, with up to 290 % photocurrent increase (J up to 100 μA cm -2 , λ >450 nm, applied bias <1.23 V vs RHE, F.E.O 2 >80 %) compared to the non-polymerized analog. Moreover, the direct PBI-quantasome polymerization on the photoanode surface was performed by light irradiation of the radical initiator 2,2'-Azobis(2-methylpropionamidine), improving the photoelectrode robustness under high solar irradiance (>8 suns) and limiting the photocurrent loss (<20 %) at 1.52 V vs RHE compared to the non-polymerized system., (© 2024 Wiley‐VCH GmbH.)

The last decade has seen a tremendous expansion of the field of heterogenized molecular catalysis, especially with the growing interest in metal-organic frameworks and related porous hybrid solids. With successful achievements in the transfer from molecular homogeneous catalysis to heterogenized processes come the necessary discussions on methodologies used and a critical assessment on the advantages of heterogenizing molecular catalysis. Here we use the example of nickel-catalyzed ethylene oligomerization, a reaction of both fundamental and applied interest, to review heterogenization methodologies of well-defined molecular catalysts within porous solids while addressing the biases in the comparison between original molecular systems and heterogenized counterparts.

The catalytic activity of multifunctional, microporous materials is directly linked to the spatial arrangement of their structural building blocks. Despite great achievements in the design and incorporation of isolated catalytically active metal complexes within such materials, a detailed understanding of their atomic-level structure and the local environment of the active species remains a fundamental challenge, especially when these latter are hosted in non-crystalline organic polymers. Here, we show that by combining computational chemistry with pair distribution function analysis, 129 Xe NMR, and Dynamic Nuclear Polarization enhanced NMR spectroscopy, a very accurate description of the molecular structure and confining surroundings of a catalytically active Rh-based organometallic complex incorporated inside the cavity of amorphous bipyridine-based porous polymers is obtained. Small, but significant, differences in the structural properties of the polymers are highlighted depending on their backbone motifs., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Metal-organic frameworks are a class of porous materials that show promising properties in the field of microelectronics. To reach industrial use of these materials, gas phase techniques are often preferred and were recently introduced. However, the thicknesses achieved are not sufficient, limiting further development. In this work, an improved gas phase process allowing ZIF-8 layer formation of several hundreds of nm using cyclic ligand/water exposures is described. Then, by a combination of in-depth surface analyses and molecular dynamics simulations, the presence and role of hydroxyl defects in the ZIF-8 layer to reach this thickness are established. At the same time, this study unveils an inherent limit of the method: thickness growth is consubstantial with defect repairing upon the crystallites ripening; such defect repairing eventually leads to the decrease of the pore window below the diffusion radius of the incoming linker, thus apparently capping the maximum MOF thickness observable for this type of material topology through this growth method.

An earth-abundant nickel(II) bipyridine catalyst, combined with lithium hexamethyldisilazide as base, demonstrates its wide applicability in the direct arylation polymerization of di- and tri-thiophene heteroaryls with poly(hetero)aryl halides. With a nickel catalyst loading of 2.5 mol%, a series of twenty highly cross-linked organic polymers is obtained in 34 to 99 % yields. Using mixed polytopic coupling partners allows obtaining alternating and optically active thiophene-based solids with intrinsic porosity., (© 2022 Wiley-VCH GmbH.)

Covalent triazine frameworks (CTFs) are a class of porous organic polymers that continuously attract growing interest because of their outstanding chemical and physical properties. However, the control of extended porous organic framework structures at the molecular scale for a precise adjustment of their properties has hardly been achieved so far. Here, we present a series of bipyridine-based CTFs synthesized through polycondensation, in which the sequence of specific building blocks is well controlled. The reported synthetic strategy allows us to tailor the physicochemical features of the CTF materials, including the nitrogen content, the apparent specific surface area, and optoelectronic properties. Based on a comprehensive analytical investigation, we demonstrate a direct correlation of the CTF bipyridine content with the material features such as the specific surface area, band gap, charge separation, and surface wettability with water. The entirety of these parameters dictates the catalytic activity as demonstrated for the photocatalytic hydrogen evolution reaction (HER). The material with the optimal balance between optoelectronic properties and highest hydrophilicity enables HER production rates of up to 7.2 mmol/(h·g) under visible light irradiation and in the presence of a platinum cocatalyst.

Heterogenization of molecular catalysts via their immobilization within extended structures often results in a lowering of their catalytic properties due to a change in their coordination sphere. Metal-organic polyhedra (MOP) are an emerging class of well-defined hybrid compounds with a high number of accessible metal sites organized around an inner cavity, making them appealing candidates for catalytic applications. Here, we demonstrate a design strategy that enhances the catalytic properties of dirhodium paddlewheels heterogenized within MOP (Rh-MOP) and their three-dimensional assembled supramolecular structures, which proved to be very efficient catalysts for the selective photochemical reduction of carbon dioxide to formic acid. Surprisingly, the catalytic activity per Rh atom is higher in the supramolecular structures than in its molecular sub-unit Rh-MOP or in the Rh-metal-organic framework (Rh-MOF) and yields turnover frequencies of up to 60 h -1 and production rates of approx. 76 mmole formic acid per gram of the catalyst per hour, unprecedented in heterogeneous photocatalysis. The enhanced catalytic activity is investigated by X-ray photoelectron spectroscopy and electrochemical characterization, showing that self-assembly into supramolecular polymers increases the electron density on the active site, making the overall reaction thermodynamically more favorable. The catalyst can be recycled without loss of activity and with no change of its molecular structure as shown by pair distribution function analysis. These results demonstrate the high potential of MOP as catalysts for the photoreduction of CO 2 and open a new perspective for the electronic design of discrete molecular architectures with accessible metal sites for the production of solar fuels.

The occurrence of metabolic acidosis with increased anion gap in the context of chronic paracetamol intoxication is an easily treatable clinical situation. Its rapid recognition is essential given its complete reversibility in the event of adequate management by eviction of the toxic agent, in this case paracetamol. It has an unknown cause and therefore potentially under-diagnosed, to be considered in the same way as the other more frequent etiologies. Because of this lack of knowledge, its frequency is probably underestimated considering the widespread consumption of paracetamol in the population.

Intubation followed by mechanical ventilation is a classic technic for managing severe respiratory failure in hospital practice. Far from being exempted of risks, this technic can lead to serious complications. We hereby present illustrating images of a complication directly linked to the non-physiological respiratory mode on which mechanical ventilation is based, namely barotrauma linked to positive ventilatory pressures.

Understanding and controlling molecular recognition mechanisms at a chiral solid interface is a continuously addressed challenge in heterogeneous catalysis. Here, the molecular recognition of a chiral peptide-functionalized metal-organic framework (MOF) catalyst towards a pro-chiral substrate is evaluated experimentally and in silico . The MIL-101 metal-organic framework is used as a macroligand for hosting a Noyori-type chiral ruthenium molecular catalyst, namely (benzene)Ru@MIL-101-NH-Gly-Pro. Its catalytic perfomance toward the asymmetric transfer hydrogenation (ATH) of acetophenone into R - and S -phenylethanol are assessed. The excellent match between the experimentally obtained enantiomeric excesses and the computational outcomes provides a robust atomic-level rationale for the observed product selectivities. The unprecedented role of the MOF in confining the molecular Ru-catalyst and in determining the access of the prochiral substrate to the active site is revealed in terms of highly face-specific host-guest interactions. The predicted surface-specific face differentiation of the prochiral substrate is experimentally corroborated since a three-fold increase in enantiomeric excess is obtained with the heterogeneous MOF-based catalyst when compared to its homogeneous molecular counterpart., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The molecular-level structuration of two full photosystems into conjugated porous organic polymers is reported. The strategy of heterogenization gives rise to photosystems which are still fully active after 4 days of continuous illumination. Those materials catalyze the carbon dioxide photoreduction driven by visible light to produce up to three grams of formate per gram of catalyst. The covalent tethering of the two active sites into a single framework is shown to play a key role in the visible light activation of the catalyst. The unprecedented long-term efficiency arises from an optimal photoinduced electron transfer from the light harvesting moiety to the catalytic site as anticipated by quantum mechanical calculations and evidenced by in situ ultrafast time-resolved spectroscopy., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In December 2019, in Wuhan, a new human infectious pathology was born, COVID-19, consisting above all in pneumoniae, induced by the coronavirus named SARS-CoV-2 because of the respiratory distress it caused (SARS for severe acute respiratory syndrome, and CoV for Coronavirus). A real health and planetary crisis has appeared, much more substantial than that linked to SARS-CoV-1 in 2002-2004 and to MERS-CoV (Middle East Respiratory Syndrome Coronavirus) in 2012. In addition to respiratory damage that can be dramatic, this pathology is complicated by the frequency of cardiovascular, renal and coagulation diseases. Health care systems have had to adapt urgently, in the absence of hindsight from the pathology, and without effective therapeutic weapons. Through this review of the literature, we detail our local practices for the overall management of patients hospitalized in Intensive care.

Since its first description in 1967, a lot of progress has been made in understanding the pathophysiology, diagnosis and management of acute respiratory distress syndrome (ARDS). This nosological entity is based on the appearance of a diffuse alveolar damage associating pulmonary epithelial barrier disruption with an alveolar filling, both responsible of profound hypoxemia and important morbi-mortality. Nowadays, ARDS remains a frequent syndrome, associated with various etiologies. Diagnosis is based on the occurrence of acute hypoxic respiratory failure not explained by cardiac insufficiency or volume overload, within 7 days after a recognized risk factor, and in the presence of bilateral pulmonary opacities not fully explained by effusions, atelectasis or nodules on the chest radiography. Survivors present an increased risk of developing cognitive decline, depression, post-traumatic stress, and typical ICU related side-effects such as polyneuropathy and sarcopenia. In this context and not withstanding significant recent progress in the field of mechanical ventilation and extra-corporeal respiratory assistance, early diagnosis remains essential to identify patients with ARDS in order to offer them the most appropriate therapy.

A molecular catalyst [Cp*Rh(4,4'-bpydc)] 2+ and a molecular photosensitizer [Ru(bpy) 2 (4,4'-bpydc)] 2+ (bpydc=bipyridinedicarboxylic acid) were co-immobilized into the highly porous metal-organic framework MIL-101-NH 2 (Al) upon easy postsynthetic impregnation. The Rh-Ru@MIL-101-NH 2 composite allows the reduction of CO 2 under visible light, while exhibiting remarkable selectivity with the exclusive production of formate. This Rh-Ru@MIL-101-NH 2 solid represents the first example of MOFs functionalized with both a catalyst and a photosensitizer in a noncovalent fashion. Thanks to the coconfinement of the catalyst and photosensitizer into the cavity's nanospace, the MOF pores are used as nanoreactors and enable molecular catalysis in a heterogeneous manner., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Acetaminophen is the most consumable analgesic in the world in the form of medical prescription or self-medication. It is one of the active ingredients most often involved in voluntary poisoning. Lethal dose of acetaminophen classically induces acute hepatic failure on hepatic necrosis. Chronic intake of sub-lethal doses (i.e. near recommended therapeutic doses) of acetaminophen in the presence of certain risk factors may be responsible for another much less recognized pathological manifestation: severe metabolic acidosis with an increased anion gap due to the accumulation of 5-oxoproline or pyroglutamic acid.

The addition of a CO 2 -adsorption component (substituted imidazolate-based SIM-1 crystals) to a gas-diffusion layer-type catalytic electrode enhances the activity and especially the selectivity towards >C1 carbon chain products (ethanol, acetone, and isopropanol) of a Pt-based electrocatalyst that is not able to form products of CO 2 reduction involving C-C bond formation under conventional (liquid-phase) conditions. This indicates that the increase of the effective CO 2 concentration at the electrode active surface is the factor controlling the formation of >C1 products rather than only the intrinsic properties of the electrocatalyst., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Photoacoustic Fourier-transform infrared spectroscopy makes it possible to determine the organic composition of mixed-linker metal-organic frameworks. The sound produced upon IR irradiation enables the discrimination of azido and amino linkers in three different MOF platforms with a sensitivity that is two orders of magnitude higher than that achieved using classic IR analysis., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)