Tubular Structures of Calcium Carbonate: Formation,Characterization, and Implications in Natural Mineral Environments

Chemical gardens are self-assembled tubular precipitates formed by a combination of osmosis, buoyancy, and chemical reaction, and thought to be capable of catalyzing prebiotic condensation reactions. In many cases, the tube wall is a bilayer structure with the properties of a diaphragm and/or a membrane. The interest in silica gardens as microreactors for materials science has increased over the past decade because of their ability to create long-lasting electrochemical potential. In this study, we have grown single macroscopic tubes based on calcium carbonate and monitored their time-dependent behavior by in situ measurements of pH, ionic concentrations inside and outside the tubular membranes, and electrochemical potential differences. Furthermore, we have characterized the composition and structure of the tubular membranes by using ex situ X-ray diffraction, infrared and Raman spectroscopy, as well as scanning electron microscopy. Based on the collected data, we propose a physicochemical mechanism for the formation and ripening of these peculiar CaCO₃ structures and compare the results to those of other chemical garden systems. We find that the wall of the macroscopic calcium carbonate tubes is a bilayer of texturally distinct but compositionally similar calcite showing high crystallinity. The resulting high density of the material prevents macroscopic calcium carbonate gardens from developing significant electrochemical potential differences. In the light of these observations, possible implications in materials science and prebiotic (geo)chemistry are discussed.     

Effect of Arylmethylene Substitutions on Molecular Structure,Optoelectronic Properties and Photovoltaic Performance of Dithienocyclopentafluorene-Based Small-Molecule Acceptors

Two dithienocyclopentafluorene-based small-molecule acceptors (SMAs) were developed that feature methylene-functionalized conjugated side chains, to study the effect of arylmethylene substitution and its number on structure, optoelectronic properties and device performance. Results showed that two SMAs have better absorption properties and planarity, lower bandgaps and higher LUMOs compared with the control SMA without conjugated side chains. The synthesized SMAs were tested in polymer solar cells for examples of their applicability. This work argues that the introduction of methylene-functionalized conjugated side chains has great potential in tuning molecular structure, optoelectronic properties, device physics and photovoltaic performance of SMAs.     

Modulating the Acidic and Basic Site Concentration of Metal-Organic Framework Derivatives to Promote the Carbon Dioxide Epoxidation Reaction

Metal-organic framework (MOF) is an ideal precursor/template for porous carbon, and its active components are uniformly doped, which can be used in energy storage and catalytic conversion fields. Metal-organic framework PCN-224 with carboxylporphyrin as the ligand was synthesized, and then Zn²⁺ and Co²⁺ ions were coordinated in the center of the porphyrin ring by post-modification. Here, PCN-224−ZnCo with different ratios of bimetallic Zn²⁺/Co²⁺ ions were used as the precursor, and the metal-nitrogen-carbon(M−N−C) material of PCN-224−ZnCo-950 was obtained by pyrolyzing the precursor at 950 °C in Ar. Because Zn is easy to volatilize at 950 °C, the formed M−N−C materials can reflect different Co contents and different basic site concentrations. The formed material still maintains the original basic framework. With the increase of Zn²⁺/Co²⁺ ratio in precursor, the concentration of N-containing alkaline sites in pyrolysis products gradually increase. Compared with the precursor, PCN-224−ZnCo₁-950 with Zn²⁺/Co²⁺=1 : 1 has greatly improved basicity and suitable acidic/ alkaline site concentration. It can be efficiently used to carbon dioxide absorption and catalyze the cycloaddition of CO₂ with epoxide. More importantly, the current method of adjusting the acidic/basic sites in M−N−C materials through volatilization of volatile metals can provide an effective strategy for adjusting the catalysis of MOF derivatives with porphyrin structure.     

Heterogeneous Catalysis and Parahydrogen-Induced Polarization

Parahydrogen-induced polarization with heterogeneous catalysts (HET-PHIP) has been a subject of extensive research in the last decade since its first observation in 2007. While NMR signal enhancements obtained with such catalysts are currently below those achieved with transition metal complexes in homogeneous hydrogenations in solution, this relatively new field demonstrates major prospects for a broad range of advanced fundamental and practical applications, from providing catalyst-free hyperpolarized fluids for biomedical magnetic resonance imaging (MRI) to exploring mechanisms of industrially important heterogeneous catalytic processes. This review covers the evolution of the heterogeneous catalysts used for PHIP observation, from metal complexes immobilized on solid supports to bulk metals and single-atom catalysts and discusses the general visions for maximizing the obtained NMR signal enhancements using HET-PHIP. Various practical applications of HET-PHIP, both for catalytic studies and for potential production of hyperpolarized contrast agents for MRI, are described.     

Die Ringinversions-Barriere in [2.2]Metacyclophan

From racemization studies on optically active [2.2]metacyclophanes substituted in position 4, the parameters of activation for the inversion of the tenmembered ring were found to be: G ₄₂₃ =31.5 kcal/mole, H =27.5 kcal/mole and S =–10 Cl/mole.Racemization does not occurvia bond forming or breaking; the value for the inversion barrier is not affected by substituents in position 4 and therefore corresponds to the value of unsubstituted [2.2]metacyclophane, whereas substituents in the bridge exert a distinct influence. These results can easily be explained on the basis of the isoconformational concept.

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Mit 5 Abbildungen

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Herrn Prof. Dr.O. Hoffmann-Ostenhof mit besten Wünschen zum 60. Geburtstag gewidmet.     

Synthese neuer Aminofluorsilane,sowie Alkoxylierung von Bis (trimethylsilyl)-amino-fluorsilanen

The reaction of aminofluorsilanes of the type (R=H,F) (Me ₃Si)₂N?SiF₂R with two moles of ammonia, or of a mono- or dialkylamine, yields the corresponding amino-compounds, e.g. (Me ₃Si)₂N?Si(F)R?NH₂, (Me ₃Si)₂N?Si(F)R?NHR′ and (Me ₃Si)₂N?Si(F)R?NR₂′ (R′=Me, Et). Analogous products are obtained by reaction of the aminofluorosilanes with lithium salts of amines with bulky organic substituents in a 1 : 1 molar ratio. Alkoxy- and aryloxyaminofluorosilanes are prepared by the reaction of sodium alcoholates and sodium phenolate with (Me ₃Si)₂N?Si(F₂)R (R=H, C₂H₃, C₂H₅, C₆H₅). The i.r.-, mass-,¹H- and¹⁹F-NMR spectra of the above compounds are reported.     

The electronic structure of periodic protein models

The energy band structures of a two-dimensional polyformamide network have been calculated with the aid of the CNDO/2 and MINDO/2 crystal orbital method in the first neighbour's interactions approximation. For comparison also one-dimensional polyformamide chains have been computed with the same methods. The features of the obtained band structures are discussed.

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Zusammenfassung Es wurden die Energiebandenstrukturen eines zweidimensionalen Polyformamid-Netzwerkes in einer Näherung, die die Wechselwirkung der ersten Nachbarn berücksichtigt, mit Hilfe der CNDO/2 und MINDO/2 Kristallorbital-Methoden berechnet. Zum Vergleich wurden auch eindimensionale Polyformamid-Ketten unter Verwendung derselben Methoden berechnet. Die Eigenschaften der erhaltenen Bandenstrukturen werden diskutiert.

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Résumé Calcul de la structure des bandes d'énergie d'un réseau bidimensionnel de polyformamide à l'aide des méthodes d'orbitales cristallines CNDO/2 et MINDO/2 dans l'approximation d'interaction des premiers voisins. A titre de comparaison les chaînes unidimensionnelles de polyformamide ont été calculées avec les mêmes méthodes. Discussion des caractéristiques des structures de bande obtenues.