Two and multilevel spectral switching of single molecules in polystyrene at room temperature

Various switching processes with jumps between two or more spectral states were observed for single molecules of the fluorescent dyes PI and DAPI in polystyrene at room temperature. Switching processes were found in the temporal trajectories of almost each spectral parameter. Statistical analyses on the distribution of jumpwidths and on correlations between them were performed. By this means a discrimination between extrinsic and intrinsic mechanisms, which trigger the observed switching dynamic, has been possible in some cases even without anticipated assumption on the nature of the mechanism itself. It has been found that PI and DAPI behave considerably different in single molecule spectroscopy, opposed to their almost identical appearance on bulk level.     

Xenon porometry at room temperature

Xenon porometry is a method in which porous material is immersed in a medium and the properties of the material are studied by means of 129Xe nuclear magnetic resonance (NMR) of xenon gas dissolved in the medium. For instance, the chemical shift of a particular signal (referred to as signal D) arising from xenon inside small pockets formed in the pores during the freezing of the confined medium is highly sensitive to the pore size. In the present study, we show that when naphthalene is used as the medium the pore size distribution of the material can be determined by measuring a single one-dimensional spectrum near room temperature and converting the chemical shift scale of signal D to the pore radius scale by using an experimentally determined correlation. A model has been developed that explains the curious behavior of the chemical shift of signal D as a function of pore radius. The other signals of the spectra measured at different temperatures have also been identified, and the influence of xenon pressure on the spectra has been studied. For comparison, 129Xe NMR spectra of pure xenon gas adsorbed to porous materials have been measured and analyzed.     

Synthesis of micro- and mesoporous molecular sieves at room temperature and neutral pH catalyzed by functional analogues of silicatein

By using functional mimics of the protein silicatein alpha together with organic structure directing agents, it was possible to produce different mesoporous and microporous molecular sieves at room temperature and neutral pH.     

Thermal properties at room temperature of polytetrafluoroethylene

Through Differential Scanning Calorimetry (DSC), at least three room temperature transitions are clearly observable for native polytetrafluoroethylene (PTFE). The influence of the thermal history on the room temperature transitions has been investigated. Possible interpretations for the lowest room temperature transition are suggested.

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Zusammenfassung Bei der Untersuchung von nativen Polytetrafluoroethylen (PTFE) lassen sich im Raumtemperaturbereich zumindest drei Umwandlungen eindeutig beobachten. Der Einfluss der termischen Vorgeschichte von PTFE Proben auf die Umwandlungen im Raumtemperaturbereich wurde untersucht.Mögliche ErklÄrungen für den tiefstliegenden übergang im genannten Temperaturbereich werden vorgeschlagen.

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Dr. G. Ajroldi and Prof. G. Guerra are gratefully acknowledged for useful advice and stimulating discussions.     

Crystallization-induced phosphorescence of benzils at room temperature

Efficient room temperature phosphorescence (RTP) is rarely observed in pure organic luminogens. However, we have newly observed that benzil and its derivatives are nonluminescent in solvents and thin layer chromatography (TLC) plates, but become highly phosphorescent in crystal state at room temperature, exhibiting typical crystallization-induced phosphorescence (CIP) characteristics. The CIP phenomenon is ascribed to the restriction of intramolecular rotations in crystals owing to effective intermolecular interactions. Such intermolecular interactions greatly rigidify the molecular conformation and significantly decrease the nonradiative deactivation channels of the triplet excitons, thus giving boosted phosphorescent emission at room temperature.     

Synthesis of zeolite nanocrystals at room temperature

Zeolite A nanoparticles were synthesized under room-temperature conditions from a very reactive organic-template-free gel system. The optimization of the syntheses parameters, namely, the composition of the initial system and the careful choice of the reactants, allowed the crystallization to be accomplished within 3 days. At this stage the individual zeolite crystals were in the range of 100-300 nm without well-developed crystal faces. The prolongation of the synthesis time up to 10 days led to formation of larger well-faceted cubic crystals averaging about 400-500 nm in size. The high-resolution transmission electron microscopy (HRTEM) study revealed that a thin layer of amorphous material covers the zeolite particles acting as a binder between individual zeolite crystals. The postsynthesis treatment of the product in NH(3) media under ultrasonic radiation disintegrated the loosely attached zeolite particles and decreased the fraction of zeolite A particles with low colloidal stability. The employed approach, however, did not result in complete disintegration of aggregated crystals. The zeolite crystals obtained under ambient conditions were characterized by XRD, SEM, dynamic light scattering, and N(2) adsorption measurements.     

Cationic polymerization of isobutylene at room temperature

This review highlights recent approaches toward polyisobutylene (PIB) by an energy efficient room temperature cationic polymerization. Special focus is laid on our own work using modified Lewis acids and nitrile‐ligated metal complexes associated with weakly coordinating anions. In both cases, suitable conditions have been found for efficient production of PIB characterized by medium to low molar masses and a high content of exo double bonds as end groups—the typical features of highly reactive PIB, an important commercial intermediate toward oil and gasoline additives. These and other approaches demonstrate that the cationic polymerization of isobutylene is still not fully explored, and new innovative catalyst systems can lead to surprising results of high commercial interest. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Hydroboration with pyridine borane at room temperature

Treatment of pyridine borane (Py.BH3) with iodine, bromine, or strong acids affords activated Py.BH2X complexes that are capable of hydroborating alkenes at room temperature. Evidence is presented for an unusual hydroboration mechanism involving leaving group displacement. In contrast to THF.BH3, hydroboration with Py.BH2I selectively affords the monoadducts. The crude hydroboration products are converted into synthetically useful potassium alkyltrifluoroborate salts upon treatment with methanolic KHF2.     

Single-molecule triplet-state photon antibunching at room temperature

We have probed single-molecule metal-to-ligand charge transfer (MLCT) dynamics of a ruthenium complex at room temperature. Using photon antibunching measurements under continuous wave (CW) laser excitation, nonclassical photon statistics, and excitation power dependent measurements, we were able to selectively measure the single-molecule MLCT state lifetime. This work demonstrated, as the first single-molecule photon antibunching measurement of the triplet excited state, a new application of single-molecule spectroscopy on excited-state dynamics and ground-state recovering dynamics of an important class of chemical species that have often been used and studied in energy conversion and electron transfer.     

Polyurethane adhesive composition cured at room temperature

The influence of polyfunctional hydroxyl-containing oligomer on the rheological, physicomechanical, and adhesive properties of polyurethane composite based on multicomponent oligomer blend and polyisocyanate is investigated. The kinetics of curing is investigated by the viscometric method, and the composition lifetime is determined. It is shown that the polyurethanes under investigation can be used as fast-curing adhesive composites of cold curing operating in a temperature interval of up to +90°C.     

Transition-metal-free C-arylation at room temperature by arynes

A facile, fluoride-induced transition-metal-free chemoselective α-arylation of β-dicarbonyl compounds (malonamide esters) at room temperature using aryne intermediates has been demonstrated. Selective mono- or diarylation and generation of a quaternary benzylic stereocenter have also been achieved. The methodology will be highly useful for the synthesis of a library of CNS depressant barbiturate drugs like Phenobarbital.     

Multiaxial ratcheting behavior of PTFE at room temperature

A series of multiaxial ratcheting experiments have been performed on polyteterafluoroethylene (PTFE) solid cylindrical specimens. All the tests were conducted under cyclic shear strain with a constant axial stress at room temperature. The effects of axial stress, shear strain range, shear strain rate and their histories on the ratcheting behavior of PTFE were studied. It is shown that the ratcheting strain depends on the constant axial stress, cyclic shear strain range and shear strain rate. The ratcheting strain increases more rapidly as the constant axial stress or shear strain range become larger, or the shear strain rate is reduced. Furthermore, the loading histories also play an important role in the progress of ratcheting. The prior cycling with higher axial stress, larger strain range or lower strain rate greatly restrains ratcheting strain of subsequent cycling at lower strains. Such phenomenon is due to the enhancement of the material deformation resistance caused by the prior loadings.