From Enantiopure Hydroxyaldehydes to Complex Heterocyclic Scaffolds: Development of Domino Petasis/Diels–Alder and Cross‐Metathesis/Michael Addition Reactions

One‐step assembly of hexahydroisoindole scaffolds by a sequence that combines the Petasis (borono‐Mannich) and Diels–Alder reactions is described. The unique selectivity observed experimentally was confirmed by quantum calculations. The current method is applicable to a broad range of substrates, including free sugars, and holds significant potential to efficiently and stereoselectively build new heterocyclic structures. This easy and fast entry to functionalized polycyclic compounds can be pursued by further transformations, for example, additional ring closure by a cross‐metathesis/Michael addition domino sequence.     

Conversion of Mg‐Li Bimetallic Alloys to Magnesium Alkoxide and Magnesium Oxide Ceramic Nanowires

Technologically important composites with enhanced thermal and mechanical properties rely on the reinforcement by the high specific strength ceramic nanofibers or nanowires (NWs) with high aspect ratios. However, conventional synthesis routes to produce such ceramic NWs have prohibitively high cost. Now, direct transformation of bulk Mg‐Li alloys into Mg alkoxide NWs is demonstrated without the use of catalysts, templates, expensive or toxic chemicals, or any external stimuli. This mechanism proceeds through the minimization of strain energy at the boundary of phase transformation front leading to the formation of ultra‐long NWs with tunable dimensions. Such alkoxide NWs can be easily converted in air into ceramic MgO NWs with similar dimensions. The impact of the alloy grain size and Li content, synthesis temperature, inductive and steric effects of alkoxide groups on the diameter, length, composition, ductility, and oxidation of the produced NWs is discussed.     

Tuning Cellular Biological Functions Through the Controlled Release of NO from a Porous Ti‐MOF

Materials for the controlled release of nitric oxide (NO) are of interest for therapeutic applications. However, to date, many suffer from toxicity and stability issues, as well as poor performance. Herein, we propose a new NO adsorption/release mechanism through the formation of nitrites on the skeleton of a titanium‐based metal–organic framework (MOF) that we named MIP‐177, featuring a suitable set of properties for such an application: (i) high NO storage capacity (3 μmol mg^?1_solid), (ii) excellent biocompatibility at therapeutic relevant concentrations (no cytotoxicity at 90 μg mL^?1 for wound healing) due to its high stability in biological media (<9 % degradation in 72 hours) and (iii) slow NO release in biological media (≈2 hours for 90 % release). The prospective application of MIP‐177 is demonstrated through NO‐driven control of mitochondrial respiration in cells and stimulation of cell migration, paving the way for the design of new NO delivery systems for wound healing therapy.     

Probing the Brønsted Acidity of the External Surface of Faujasite-Type Zeolites

We outline two methodologies to selectively characterize the Brønsted acidity of the external surface of FAU-type zeolites by IR and NMR spectroscopy of adsorbed basic probe molecules. The challenge and goal are to develop reliable and quantitative IR and NMR methodologies to investigate the accessibility of acidic sites in the large pore FAU-type zeolite Y and its mesoporous derivatives often referred to as ultra-stable Y (USY). The accessibility of their Brønsted acid sites to probe molecules (n-alkylamines, n-alkylpyridines, n-alkylphosphine- and phenylphosphine-oxides) of different molecular sizes is quantitatively monitored either by IR or ³¹P NMR spectroscopy. It is now possible, for the first time to quantitatively discriminate between the Brønsted acidity located in the microporosity and on the external surface of large pore zeolites. For instance, the number of external acid sites on a Y (LZY-64) zeolite represents 2 % of its total acid sites while that of a USY (CBV760) represents 4 % while the latter has a much lower framework Si/Al ratio.     

Photochromic Free MOF‐Based Near‐Infrared Optical Switch

We demonstrate herein an all‐optical switch based on stimuli‐responsive and photochromic‐free metal–organic framework (HKUST‐1). Ultrafast near‐infrared laser pulses stimulate a reversible 0.4 eV blue shift of the absorption band with up to 200 s^?1 rate due to dehydration and concomitant shrinking of the structure‐forming [Cu₂C₄O₈] cages of HKUST‐1. Such light‐induced switching enables the remote modulation of intensities of photoluminescence of single crystals of HKUST‐1 as well visible radiation passing through the crystal by 2 order of magnitude. This opens up the possibility of utilyzing stimuli‐responsive MOFs for all‐optical data processing devices.     

Environmentally benign nanomixing by sonication in high-pressure carbon dioxide

Due to the increased use of nanocomposites, mixing at nanoscale has become important. Current mixing techniques can be classified into: (a) dry mixing (mechanical mixing), (b) wet mixing, and (c) simultaneous production of mixed nanoparticles (when possible). Dry mixing is in general not effective in achieving desired mixing at nanoscale, whereas wet mixing suffers from different disadvantages like nanomaterial of interest should be insoluble, has to wet the liquid, and involves additional steps of filtration and drying. This paper examines the use of pressurized carbon dioxide having high density and low viscosity to replace the liquids (e.g., n-hexane, toluene). Ultrasound is applied to the suspension of nanopowders in gaseous and supercritical carbon dioxide where high impact collisions during sonication help mixing and the final mixture is obtained by simple depressurization. The method is tested for binary mixture of alumina/silica, silica/titania, MWNT (multiwalled carbon nanotubes)/silica, and MWNT/titania. The effects of sonication intensity and pressure on the degree of mixing are studied. Comparative study is also done with liquid n-hexane as a mixing media. Quantitative characterization (e.g., mean composition standard deviation, intensity of segregation) of mixing of alumina/silica and silica/titania is done with energy-dispersive X-ray spectroscopy, and that of MWNT/silica and MWNT/titania is done using field-emission scanning electron microscopy and day-light illumination spectrophotometry. Results show that mixing in carbon dioxide at higher ultrasound amplitudes is as good as in liquid n-hexane, and the final mixed product does not contain any residual media as in the case of liquid n-hexane.