ITQ-15: the first ultralarge pore zeolite with a bi-directional pore system formed by intersecting 14- and 12-ring channels, and its catalytic implications

The pore topology of ITQ-15 zeolite consists of an ultra-large 14-ring channel that is intersected perpendicularly by a 12-ring pore; acid sites have been introduced in its framework and this unique structure shows advantages over unidirectional ultralarge pore zeolites for diffusing and reacting large molecules.     

Correction: Click activated protodrugs against cancer increase the therapeutic potential of chemotherapy through local capture and activation

Correction for ‘Click activated protodrugs against cancer increase the therapeutic potential of chemotherapy through local capture and activation’ by Kui Wu et al., Chem. Sci., 2021, 12, 1259–1271, DOI: 10.1039/D0SC06099B.

The authors regret that the reference to the bond-breaking bioorthogonal chemistry, termed ‘click-to-release’ was omitted from the original article. In addition, we would like to include a reference describing the synthesis of compound 1, which is an intermediate to the protodrugs described in the original article. These references are listed below as ref. 1 and 2.The Royal Society of Chemistry apologizes for these errors and any consequent inconvenience to authors and readers.     

Differential conductance switching of planar tunnel junctions mediated by oxidation/reduction of functionally protected ferrocene

Planar tunnel junctions were fabricated by self-assembling 1,1'- ferrocenedicarboxylic acid (FDCA) onto native oxides of thermally deposited aluminum films and subsequently depositing a second aluminum film. Junctions were characterized using Reflection-Absorption Fourier Transform Infrared Spectroscopy (RAIRS) and current-voltage (I-V) spectroscopy. Before deposition of the second aluminum film, RAIRS of FDCA and ferrocenecarboxylic acid (FCA) films revealed COO(-), C=O, and Fc ring stretching modes, indicating that both types of molecules can interact strongly with the oxide and remain intact. After deposition, systems exhibited prominent COO(-) modes and weakened C=O modes, indicating further reaction with aluminum/aluminum oxide. Fc ring modes persisted in FDCA systems but disappeared in FCA systems, suggesting that the second COOH group in the FDCA molecule can act as a protecting group for the ferrocene moiety. Cyclic I-V measurements of FDCA tunnel junction systems revealed very strong ( approximately 10-fold) hysteretic differential conductance switching that was both reversible and stable. Control measurements using as prepared junctions, as well as junctions containing 1,6-hexanedioic acid, 1,9-nonanedioic acid, 1,4-dibenzoic acid, or FCA revealed only very weak ( approximately 10%) differential conductance changes. We attribute FDCA junction switching to barrier profile modifications induced by oxidation/reduction of the functionally protected ferrocene moieties.     

Useful dual Diels-Alder behavior of 2-azetidinone-tethered aryl imines as azadienophiles or azadienes: a beta-lactam-based stereocontrolled access to optically pure highly functionalized indolizidine systems

Imines derived from 4-oxoazetidine-2-carbaldehydes have been found to be versatile Diels-Alder reagents in that they exhibit two reactivity patterns. 2-Azetidinone-tethered imines undergo diastereoselective reaction with Danishefsky's diene in the presence of different Lewis acids. The effect of the amount of catalyst on the conversion rate as well as on the product ratio has been studied. Under standard reaction conditions, indium(III) chloride and zinc(II) iodide provided the best yields, and indium(III) triflate the highest diastereoselectivity in the Lewis acid promoted aza-Diels-Alder cycloaddition. Treatment of the aforementioned imines with cyclopentadiene, 2,3-dimethyl-1,3-butadiene or 3,4-dihydro-2 H-pyran led to cycloadducts arising from inverse electron-demand condensation involving the beta-lactam-tethered aryl imine as the heterodiene component. In addition, the first methodology for preparing indolizidines from beta-lactams has been developed. This process involves amide bond cleavage of the beta-lactam ring in the aza-Diels-Alder cycloadducts with concomitant cyclization. Full chirality transfer occurs when the reaction is performed with an enantiomerically pure substrate.     

Etude MNDO des composes conjugues enneagonaux

We present MNDO calculations of a series of nine-membered conjugated compounds. The geometries have been fully optimized. Cyclononatetraenyl and benzocyclononatetraenyl anions, nonapyrrol, and nonathiophene appear to be planar aromatic compounds. Following MNDO , nonafulvene has a planar prefered conformation, but a polyenic structure, while nonafuran and cyclononatetraene are gauche molecules. The Universal Huckel Method (UHM ), a simple all valence electron empirical technique which describes σ systems using localized MO , gives, qualitatively, the same results as the MNDO method. The quantum calculation carried out with MNDO and UHM have been used to describe the physicochemical properties of ninememberedring conjugated compounds under consideration. To our knowledge, we present here the first theoretical study dealing with nine-membered conjugated molecules.     

Cycloaddition reaction of 2-azadienes derived from beta-amino acids with electron-rich and electron-deficient alkenes and carbonyl compounds. Synthesis of pyridine and 1,3-oxazine derivatives

Functionalized keto-enamines 6 were obtained by nucleophilic addition of enol ethers to the imine moiety of 2-azadienes derived from dehydroaspartic esters 4. Reactions of 2-azadiene 4c containing three electron-withdrawing substituents (CO(2)R) with enol ethers 5 in the presence of lithium perchlorate led to the formation of tetrahydropyridine derivatives 7 in a regio- and stereoselective fashion. 2H-[1,3]-oxazines 10 and pyridine derivatives 12 and 13 were obtained by heterocycloaddition reactions of electron-poor azadienes 4d-g containing two electron-withdrawing substituents (4-O(2)N-C(6)H(4), CO(2)R) in positions 1 and 4 with carbonyl derivatives (ethyl glyoxalate 9a and diethyl ketomalonate 9b) and the electron-deficient olefin tetracyanoethylene 11.     

Effect of ion pairing on steady-state voltammetric limiting currents at microelectrodes Part I. Theoretical principles

Voltammetric studies in solutions of high resistivity are facilitated by the use of microelectrodes under steady-state conditions. Such solutions are encountered with solvents of low permittivity because of the very sparing solubility of electrolytes. Moreover, in such media the supporting electrolyte, as well as the electroactive ionic species, is usually extensively ion paired. Here we predict the limiting current that will flow in these circumstances, when a monovalent ion undergoes a one-electron transfer at a hemispherical microelectrode to form a neutral product. The ion pairing equilibria are assumed to be fast but all diffusion coefficients are treated as distinct. An analytical solution is elusive in the general case, but a simple numerical procedure allows the limiting current to be predicted for any combination of the system parameters. Several special cases are also discussed, some of which yield explicit formulae for the limiting current. In a companion paper, experimental data are compared with the theoretical predictions.     

In situ monitoring of metal nanoparticle self-assembly on protein-functionalized glass by broadband optical waveguide spectroscopy

Broadband, time-resolved optical waveguide (OWG) spectroscopy has been used for in situ, real-time investigation into the self-assembly of metal nanoparticle monolayers. The OWG spectroscopy makes it possible to use the transverse electric (TE) and transverse magnetic (TM) modes to measure surface plasmon absorption of immobilized metal nanoparticles in two directions, parallel and normal to the waveguide surface. Therefore, this technique can provide direction-dependent information on the metal nanoparticles at the interface. In this paper, a 50-microm-thick glass plate was used as a slab waveguide and the kinetics of Au nanoparticle adsorption on a hemoglobin-functionalized glass substrate was examined in the early stage of self-assembly. The findings show that with the TE mode the surface plasmon resonance (SPR) behavior for immobilized Au nanoparticles is different from that with the TM mode.