Synthesis,crystal structure and docking studies of tetracyclic 10‐iodo‐1,2‐dihydroisoquinolino[2,1‐b][1,2,4]benzothiadiazine 12,12‐dioxide and its precursors

The title compound, 10‐iodo‐1,2‐dihydroisoquinolino[2,1‐b][1,2,4]benzothiadiazine 12,12‐dioxide, C₁₅H₁₁IN₂O₂S ( 8 ), was synthesized via the metal‐free intramolecular N‐iodosuccinimide (NIS)‐mediated radical oxidative sp³‐C—H aminative cyclization of 2‐(2′‐aminobenzenesulfonyl)‐1,3,4‐trihydroisoquinoline, C₁₅H₁₆N₂O₂S ( 7 ). The amino adduct 7 was prepared via a two‐step reaction, starting from the condensation of 2‐nitrobenzenesulfonyl chloride ( 4 ) with 1,2,3,4‐tetrahydroisoquinoline ( 5 ), to afford 2‐(2′‐nitrobenzenesulfonyl)‐1,3,4‐trihydroisoquinoline, C₁₅H₁₄N₂O₄S ( 6 ), in 82% yield. The catalytic hydrogenation of 6 with hydrogen gas, in the presence of 10% palladium‐on‐charcoal catalyst, furnished 7 . Products 6 – 8 were characterized by their melting points, IR and NMR (¹H and ¹³C) spectroscopy, and single‐crystal X‐ray diffraction. The three compounds crystallized in the monoclinic space group, with 7 exhibiting classical intramolecular hydrogen bonds of 2.16 and 2.26 Å. All three crystal structures exhibit centrosymmetric pairs of intermolecular C—H…π(ring) and/or π–π stacking interactions. The docking studies of molecules 6 , 7 and 8 with deoxyribonucleic acid (PDB id: 1ZEW ) revealed minor‐groove binding behaviours without intercalation, with 7 presenting the most favourable global energy of the three molecules. Nonetheless, molecule 8 interacted strongly with the DNA macromolecule, with an attractive van der Waals energy of ?15.53 kcal mol^?1.     

Mechanosensitive membrane probes: push-pull papillons

ABSTRACT

Design, synthesis and evaluation of push-pull N,N′-diphenyl-dihydrodibenzo[a,c]phenazines are reported. Consistent with theoretical predictions, donors and acceptors attached to the bent mechanophore are shown to shift absorption maxima to either red or blue, depending on their positioning in the chromophore. Redshifted excitation of push-pull fluorophores is reflected in redshifted emission of both bent and planar excited states. The intensity ratios of the dual emission in more and less polar solvents imply that excited-state (ES) planarization decelerates with increasing fluorophore macrodipole, presumably due to attraction between the wings of closed papillons. ES planarization of highly polarisable papillons is not observed in lipid bilayer membranes. All push-pull papillon amphiphiles excel with aggregation-induced emission (AIE) from bent ES as micelles in water and mechanosensitivity in viscous solvents. They are not solvatochromic and only weakly fluorescent (QY < 4%).     

Calcite Deposits Differentiate Cave from House‐Farmed Edible Bird's Nest as shown by SEM‐EDX,ATR‐FTIR and Raman Microspectroscopy

The difference between the swiftlet white edible bird's nest from limestone caves versus house‐farmed ones, especially in response to high temperature and stewing time in water where the latter type would disintegrate readily, has been a puzzle for a long time. We show that edible bird's nests from the limestone caves have calcite deposits on the surface of the nest cement as compared to the house‐farmed nests which are built by swiftlets on timber planks. The micron and sub‐micron calcite particles are seen in SEM‐EDX and further characterized by ATR‐FTIR and Raman microspectroscopy. The calcite deposits make it possible for the cave nest to retain a gelatinous texture under the harsh retort conditions at 121 °C for 20 mins in commercial bottling. We show that house‐farmed nests can be soaked in CaCl₂(aq) followed by rinsing with Na₂CO₃(aq) to grow the same calcite deposits on the nest cement with the same characteristic as cave nests. Therefore, there should no longer be a need to harvest cave nests, and we can better conserve the dwindling population and natural habitats of cave swiftlets.     

Atroposelective Synthesis of Axially Chiral N‐Arylpyrroles by Chiral‐at‐Rhodium Catalysis

A transformation of fluxional into configurationally stable axially chiral N‐arylpyrroles was achieved with a highly atroposelective electrophilic aromatic substitution catalyzed by a chiral‐at‐metal rhodium Lewis acid. Specifically, N‐arylpyrroles were alkylated with N‐acryloyl‐1H‐pyrazole electrophiles in up to 93 % yield and with up to >99.5 % ee, and follow‐up conversions reveal the synthetic utility of this new method. DFT calculations elucidate the origins of the observed excellent atroposelectivity.     

Metalla‐Assembled Electron‐Rich Tweezers: Redox‐Controlled Guest Release Through Supramolecular Dimerization

Developing methodologies for on‐demand control of the release of a molecular guest requires the rational design of stimuli‐responsive hosts with functional cavities. While a substantial number of responsive metallacages have already been described, the case of coordination‐tweezers has been less explored. Herein, we report the first example of a redox‐triggered guest release from a metalla‐assembled tweezer. This tweezer incorporates two redox‐active panels constructed from the electron‐rich 9‐(1,3‐dithiol‐2‐ylidene)fluorene unit that are facing each other. It dimerizes spontaneously in solution and the resulting interpenetrated supramolecular structure can dissociate in the presence of an electron‐poor planar unit, forming a 1:1 host–guest complex. This complex dissociates upon tweezer oxidation/dimerization, offering an original redox‐triggered molecular delivery pathway.     

2D Oligosilyl Metal–Organic Frameworks as Multi‐state Switchable Materials

We report the synthesis of a set of 2D metal–organic frameworks (MOFs) constructed with organosilicon‐based linkers. These oligosilyl MOFs feature linear Si_nMe_2n(C₆H₄CO₂H)₂ ligands (lin‐Si_n, n=2, 4) connected by Cu paddlewheels. The stacking arrangement of the 2D sheets is dictated by van der Waals interactions and is tunable by solvent exchange, leading to reversible structural transformations between many crystalline and amorphous phases.     

Detection of innersphere interactions between magnesium hydrate and the phosphate backbone of the HDV ribozyme using Raman crystallography

A Raman microscope and Raman difference spectroscopy are used to detect the vibrational signature of RNA-bound magnesium hydrate in crystals of hepatitis delta virus (HDV) ribozyme and to follow the effects of magnesium hydrate binding to the nonbridging phosphate oxygens in the phosphodiester backbone. There is a correlation between the Raman intensity of the innersphere magnesium hydrate signature peak, near 322 cm-1, and the intensity of the PO2- symmetric stretch, near 1100 cm-1, perturbed by magnesium binding, demonstrating direct observation of -PO2-...Mg2+(H2O)x innersphere complexes. The complexes may be pentahydrates (x = 5) and tetrahydrates (x = 4). The assignment of the Raman feature near 322 cm-1 to a magnesium hydrate species is confirmed by isotope shifts observed in D2O and H218O that are semiquantitatively reproduced by calculations. The standardized intensity changes in the 1100 cm-1 PO2- feature seen upon magnesium hydrate binding indicates that there are approximately 5 innersphere Mg2+...-O2P contacts per HDV molecule when the crystal is exposed to a solution containing 20 mM magnesium.     

A combined spectroscopic and theoretical study of dibutyltin diacetate and dilaurate in supercritical CO2

Two organotin catalysts, namely, dibutyltin dilaurate (DBTDL) and dibutyltin diacetate (DBTDA), commonly used in the synthesis of polyurethanes, have been investigated combining vibrational spectroscopic measurements with molecular modeling. The structure and vibrational spectra of the DBTDA molecule have been simulated using density functional theory. Thus, because of the Sn...O interactions, the lowest energy conformer reveals an asymmetrically chelated structure of the acetate groups with a C2v symmetry. The experimental IR spectra of DBTDA and DBTDL diluted in carbon tetrachloride and in supercritical CO2 show unambiguously that these molecules adopt the asymmetrically chelated conformation in the solvent. A new attribution of the main peaks constituting the respective IR spectra of the catalysts could be carried out. Finally, from the IR spectra of the two catalysts diluted in supercritical CO2 reported as a function of time, it was found that both molecules react slightly with CO2. However, their spectrum remains unchanged at the earliest stage of the polymerization, indicating that these molecules preserve a catalytic activity similar to that noted in conventional organic solvent.     

Oxidation of CO by aluminum oxide cluster ions in the gas phase

Small aluminum oxide cluster cations and anions, produced by laser vaporization, were investigated regarding their reactivity toward CO and N2O employing guided-ion-beam mass spectrometry. Clusters with the same stoichiometry as bulk alumina, Al2O3, exhibited atomic oxygen transfer products when reacted with CO, suggesting the formation of CO2. Anionic clusters were less reactive than cations but showed higher selectivity towards the transfer of only a single oxygen atom. Cationic clusters, in contrast, exhibited additional products corresponding to the sequential transfer of two oxygen atoms and the loss of an aluminum atom. To determine if these stoichiometric clusters could be generated from oxygen-deficient species, clusters having a stoichiometry with one less oxygen atom than bulk alumina, Al2O2, were reacted with N2O. Cationic clusters were found to be selectively oxidized to Al2O3(+), while anionic clusters added both one and two oxygen atoms forming Al2O3(-) and Al2O4(-). The oxygen-rich Al2O4(-) cluster exhibited comparable reactivity to Al2O3(-) when reacted with CO.     

Evaluation of a new matrix-free laser desorption/ionization method through statistic studies: comparison of the DIAMS (desorption/ionization on self-assembled monolayer surface) method with the MALDI and TGFA-LDI techniques

This work demonstrates that the desorption/ionization on self-assembled monolayer surface (DIAMS) mass spectrometry, a recent matrix-free laser desorption/ionization (LDI) method based on an organic target plate, is as statistically repeatable and reproducible as matrix assisted laser desorption ionization (MALDI) and thin gold film-assisted laser desorption/ionization (TGFA-LDI) mass spectrometries. On lipophilic DIAMS of target plates with a mixture of glycerides, repeatability/reproducibility has been estimated at 15 and 30% and the relative detection limit has been evaluated at 0.3 and 3 pmol, with and without NaI respectively. Salicylic acid and its d(6)-isomer analysis confirm the applicability of the DIAMS method in the detection of compounds of low molecular weight.