Aluminum Redistribution during the Preparation of Hierarchical Zeolites by Desilication

A literature survey reveals a prominent reduction in the concentration of Brønsted acid sites in hierarchically organized zeolites with increasing mesoporous or external surface area independent of the framework type or synthesis route; this suggests a common fundamental explanation. To determine the cause, nature, and impact of the underlying changes in aluminum speciation, this study combines a multitechnique analysis that integrates basic characterization, a detailed synchrotron XRD and multiple‐quantum NMR spectroscopy assessment, and catalytic tests to correlate evolution of the properties with performance during successive steps in the preparation of hierarchical MFI‐type zeolites by desilication. The findings, subsequently generalized to FAU‐ and BEA‐type materials, identify the crucial impact of calcination on the protonic form, which is an integral step in the synthesis and regeneration of zeolite catalysts; on aluminum coordination; and the associated acidity trends.     

Ionothermal synthesis and structure analysis of an open-framework zirconium phosphate with a high CO2/CH4 adsorption ratio

Less is more: an open-framework zirconium phosphate with unusual 7-ring channels was synthesized ionothermally from a deep-eutectic solvent. This small-pore material displays a CO(2)/CH(4) adsorption ratio (17.3 at 1 bar) that is significantly higher than that of typical 8-ring materials, making it highly attractive for CO(2)/CH(4) separations.     

Metal Coordination Induced π-Extension and Triplet State Production in Diketopyrrolopyrrole Chromophores

Triplet state photophysics has been generated in two distinct diketopyrrolopyrrole (DPP) chromophores terminated with either phenyl (1) or thienyl (2) spacers, when sandwiched between two Ir(III) complexes using bipyridyl linkers. Upon coordination of the bpy-DPP-bpy subunit resulting in its planarization, the π-conjugation in the DPP chromophore formally extends and was manifested as a substantial red shift in the absorption and fluorescence profiles of 1 and 2. Low energy excitation of these dinuclear metal complexes produced strongly quenched singlet fluorescence, generated quite intense long-lived (τ ～ 3 μs) absorption transients in the red, sensitized (1)O(2) photoluminescence centered at 1270 nm in aerated solutions, and yielded low temperature near-IR phosphorescence in 1 centered at 950 nm.     

Ligand-Localized Triplet-State Photophysics in a Platinum(II) Terpyridyl Perylenediimideacetylide

The synthesis, electrochemistry, and photophysical behavior of a Pt(II) terpyridyl perylenediimide (PDI) acetylide (1) charge-transfer complex is reported. The title compound exhibits strong (ε ≈ 5 × 10(4) M(-1)cm(-1)) low-energy PDI acetylide-based π-π* absorption bands in the visible range extending to 600 nm, producing highly quenched singlet fluorescence (Φ = 0.014 ± 0.001, τ = 109 ps) with respect to a nonmetalated PDI model chromophore. Nanosecond transient absorption spectroscopy revealed the presence of a long excited-state lifetime (372 ns in 2-methyltetrahydrofuran) with transient features consistent with the PDI-acetylide triplet state, ascertained by direct comparison to a model Pt(II) PDI-acetylide complex lacking low-energy charge-transfer transitions. For the first time, time-resolved step-scan FT-IR spectroscopy was used to characterize the triplet excited state of the PDI-acetylide sensitized in the title compound and its associated model complex. The observed red shifts (～30-50 cm(-1)) in the C═O and C≡C vibrations of the two Pt(II) complexes in the long-lived excited state are consistent with formation of the (3)PDI acetylide state and found to be in excellent agreement with the expected change in the relevant DFT-calculated IR frequencies in the nonmetalated PDI model chromophore (ground singlet state and lowest triplet excited state). Formation of the PDI triplet excited state in the title chromophore was also supported by sensitization of the singlet oxygen photoluminescence centered at ～1275 nm in air-saturated acetonitrile solution, Φ((1)O(2)) = 0.52. In terms of light emission, only residual PDI-based red fluorescence could be detected and no corresponding PDI-based phosphorescence was observed in the visible or NIR region at 298 or 77 K in the Pt(II) terpyridyl perylenediimideacetylide.     

Dondorff rings: synthesis, isolation, and properties of 60°-directed bisterpyridine-based folded tetramers

Square feat: The synthesis, isolation, and characterization of five novel bisterpyridine-based metallomacrocycles, possessing a folded tetrameric configuration is reported. The initial dimeric building block with the stable linear {tpy-Ru(II) -tpy} connectivity circumvents the formation of the thermodynamically favored molecular triangles.     

Imperative programs as proofs via game semantics

Game semantics extends the Curry–Howard isomorphism to a three-way correspondence: proofs, programs, strategies. But the universe of strategies goes beyond intuitionistic logics and lambda calculus, to capture stateful programs. In this paper we describe a logical counterpart to this extension, in which proofs denote such strategies. The system is expressive: it contains all of the connectives of Intuitionistic Linear Logic, and first-order quantification. Use of Laird?s sequoid operator allows proofs with imperative behaviour to be expressed. Thus, we can embed first-order Intuitionistic Linear Logic into this system, Polarized Linear Logic, and an imperative total programming language.     

18O kinetic isotope effects in non-heme iron enzymes: probing the nature of Fe/O2 intermediates

Contrasted here are the competitive 18O/16O kinetic isotope effects (18O KIEs) on kcat/Km(O2) for three non-heme iron enzymes that activate O2 at an iron center coordinated by a 2-His-1-carboxylate facial triad: taurine dioxygenase (TauD), (S)-(2)-hydroxypropylphosphonic acid epoxidase (HppE), and 1-aminocyclopropyl-1-carboxylic acid oxidase (ACCO). Measured 18O KIEs of 1.0102 +/- 0.0002 (TauD), 1.0120 +/- 0.0002 (HppE), and 1.0215 +/- 0.0005 (ACCO) suggest the formation in the rate-limiting step of O2 activation of an FeIII-peroxohemiketal, FeIII-OOH, and FeIV O species, respectively. The comparison of the measured 18O KIEs with calculated or experimental 18O equilibrium isotope effects (18O EIEs) provides new insights into the O2 activation through an inner-sphere mechanism at a non-heme iron center.