Biosensing by Tandem Reactions of Structure Switching,Nucleolytic Digestion,and DNA Amplification of a DNA Assembly

ϕ29 DNA polymerase (ϕ29DP) is able to carry out repetitive rounds of DNA synthesis using a circular DNA template by rolling circle amplification (RCA). It also has the ability to execute 3′–5′ digestion of single‐stranded but not double‐stranded DNA. A biosensor engineering strategy is presented that takes advantage of these two properties of ϕ29DP coupled with structure‐switching DNA aptamers. The design employs a DNA assembly made of a circular DNA template, a DNA aptamer, and a pre‐primer. The DNA assembly is unable to undergo RCA in the absence of cognate target owing to the formation of duplex structures. The presence of the target, however, triggers a structure‐switching event that causes nucleolytic conversion of the pre‐primer by ϕ29DP into a mature primer to facilitate RCA. This method relays target detection by the aptamer to the production of massive DNA amplicons, giving rise to dramatically enhanced detection sensitivity.     

Low‐Dimensional Organic Tin Bromide Perovskites and Their Photoinduced Structural Transformation

Hybrid organic–inorganic metal halide perovskites possess exceptional structural tunability, with three‐ (3D), two‐ (2D), one‐ (1D), and zero‐dimensional (0D) structures on the molecular level all possible. While remarkable progress has been realized in perovskite research in recent years, the focus has been mainly on 3D and 2D structures, with 1D and 0D structures significantly underexplored. The synthesis and characterization of a series of low‐dimensional organic tin bromide perovskites with 1D and 0D structures is reported. Using the same organic and inorganic components, but at different ratios and reaction conditions, both 1D (C₄N₂H₁₄)SnBr₄ and 0D (C₄N₂H₁₄Br)₄SnBr₆ can be prepared in high yields. Moreover, photoinduced structural transformation from 1D to 0D was investigated experimentally and theoretically in which photodissociation of 1D metal halide chains followed by structural reorganization leads to the formation of a more thermodynamically stable 0D structure.     

Conformationally Flexible Bis(9‐fluorenylidene)porphyrin Diradicaloids

A stable 5,10‐bis(9‐fluorenylidene)porphyrin (Por‐Fl) diradicaloid was synthesized. It shows a quinoidal, saddle‐shaped geometry in the single crystal but can be thermally populated to a triplet diradical both in solution and in the solid state. Coordination with the Ni²⁺ ion (Por‐Fl‐Ni) does not significantly change the contorted conformation but reduces the singlet–triplet gap. Heat‐induced geometric change can explain the observed paramagnetic properties as well as unusual hysteresis in SQUID measurements. On the other hand, protonation (Por‐Fl‐2H⁺) dramatically changes the conformation while maintains the closed‐shell electronic structure. Our studies demonstrate how heat, coordination, and protonation affect the geometry, diradical character, and physical properties of conformationally flexible open‐shell singlet diradicaloids.     

Ein Polarimeter zur Messung schneller chemischer Reaktionen

Zusammenfassung Es wird ein Polarimeter vorgestellt, das die Messung schneller Änderungen der optischen Drehung gestattet. Als Meßprinzip wird eine Art Zweistrahlverfahren benutzt. Die Drehung wird in ein Signal umgesetzt, das dieser Drehung direkt proportional ist und das zur Kompensation dieser Drehung verwendet wird. Durch das Kompensationsverfahren bleibt die Messung der optischen Drehung unbeeinflußt von eventuell gleichzeitig stattfindenden Extinktionsänderungen. Die Zeitkonstante des Gerätes beträgt etwa 20 s. Die Auflösung ist durch das Schrotrauschen begrenzt und beträgt bei der angegebenen Zeitkonstante etwa ± 15 Milligrad.Wir danken der Deutschen Forschungsgemeinschaft für die Förderung dieser Untersuchungen.     

Control of Intramolecular Hydrogen Bonding in a Conformation-Switchable Helical-Spring Polymer by Solvent and Temperature

A substituted poly(phenylacetylene) derivative (PPA_HB) with two hydroxymethyl groups at the meta position of the side phenyl ring was examined as a conformation-switchable helical spring polymer that responds to solvent and heat stimuli in a precisely controlled manner. Intramolecular hydrogen bonds, which cause the helical structure of the polymer, were broken and re-formed by adjusting the hydrogen-bonding strength values (pK_HB) of various combinations of solvents or by varying the temperature. In this process, a reversible conformational change from cis–cisoid to cis–transoid, accompanied by a phase transition in the form of a helix-coil transformation occurred, with the polymer exhibiting critical changes of color fading and recovery in specific environments. These results demonstrate that PPA_HB can be used as either a pK_HB indicator or a thermometer. The color changes of the polymer solution are described in detail based on spectroscopic analyses and thermodynamic considerations.     

Ansprechzeiten an Festk?rpermembranelektroden (I?, Cl?) bei schnellen Konzentrations?nderungen in str?menden L?sungen

Zusammenfassung Es wurde der Einfluß verschiedener experimenteller Parameter, wie Konzentrationsverhältnis, Endkonzentration, Richtung der Konzentrationsänderung, Konditionierung und Oberflächenbehandlung, Temperatur, Ionenstärke und Viskosität auf die Ansprechzeiten von Festkörpermembranelektroden untersucht.

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Response time of solid-state membrane electrodes (I^–, Cl^–) under fast changes of concentration in streaming solutions

Summary The influence of different experimental parameters like concentration ratio, final concentration, direction of concentration change, conditioning and surface treatment of the electrodes, temperature, ionic strength and viscosity on the response time of solid-state membrane electrodes is described.

Die vorliegende Untersuchung wurde in dankenswerter Weise durch Mittel der Deutschen Forschungsgemeinschaft und des Verbandes der chemischen Industrie unterstützt.     

A Vesicle‐to‐Worm Transition Provides a New High‐Temperature Oil Thickening Mechanism

Diblock copolymer vesicles are prepared via RAFT dispersion polymerization directly in mineral oil. Such vesicles undergo a vesicle‐to‐worm transition on heating to 150 °C, as judged by TEM and SAXS. Variable‐temperature ¹H NMR spectroscopy indicates that this transition is the result of surface plasticization of the membrane‐forming block by hot solvent, effectively increasing the volume fraction of the stabilizer block and so reducing the packing parameter for the copolymer chains. The rheological behavior of a 10 % w/w copolymer dispersion in mineral oil is strongly temperature‐dependent: the storage modulus increases by five orders of magnitude on heating above the critical gelation temperature of 135 °C, as the non‐interacting vesicles are converted into weakly interacting worms. SAXS studies indicate that, on average, three worms are formed per vesicle. Such vesicle‐to‐worm transitions offer an interesting new mechanism for the high‐temperature thickening of oils.