Intrinsic lifetimes of the excited state of DNA and RNA bases

The lifetimes of the excited state of free nucleobases were measured in the gas phase for the first time. They are, respectively, 1.0 and 0.8 ps for the purine bases adenine (shown above) and guanine and 3.2, 2.4, and 6.4 ps for the pyrimidine bases cytosine, uracil, and thymine at 267 nm. The longer lifetimes of the pyrimidine bases may be associated with their higher propensity toward photodegradation, especially in the case of thymine. The ultrashort lifetime of nucleobases conventionally known in solution was found to be an intrinsic molecular property due to extremely facile internal conversion, and therefore the lifetime should be largely independent of the medium at this energy, that is, whether in vacuo, in solution, or in vivo. The evolutionary selection of nucleobases as the durable carriers of genetic information is suggested to be due to their inherent immunity from photochemical reactions.     

The Fluorescence of native DNA at room temperature

The fluorescence spectra (300–500nm) quantum yields (φ_f) and excitation spectra (240–285 nm) are reported for neutral aqueous sloutions of purified native DNA from calf thymus, E. coli bacterium, and hen erythrocyte near 20°C. The same properties were also measured for a reference solution of mononucleotides, and direct comparisons were made. Whether purified or not, the DNA spectra all closely resemble that from the monomer mixture between 300 and 360 nm but shows a broad, low level shoulder at λ_max ≈ 450nm which is absent in the monomer spectrum. The φ_f for the purified DNA is (4 = 1) x 10^-5, about half that of the monomer reference solution and unpurified DNA. The excitation spectrum is slightly red-shifted from the absorption for both the DNA and the monomer mixture, but not for the individual monomers. The fluorescence exhibits abrupt changes associated with the denaturation of DNA at ≈ 80°C and pII) <4 or > 11.     

Magnetic resonance of short-lived triplet exciton pairs detected by fluorescence modulation at room temperature

The possibility of resonant electromagnetic field modulation of the rate of reactions between paramagnetic particles in a condensed medium lasting for 10^?8–10^?10 sand shorter than the spin-lattice relaxation time has been demonstrated experimentally. The EPR spectra of triplet exciton pairs in tetracene and charge transfer crystals have been recorded at room temperature.     

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.     

Twisted internal charge transfer fluorescence of para-N,N-dimethylaminobenzonitrile in rigid matrix at room temperature

The dual fluorescence of para-N,N-dimethylaminobenzonitrile is observed for the first time in a rigid matrix at room temperature (polyvinylalcohol). A relationship between the twisted internal charge transfer (TICT) fluorescence and the formation of a ground-state hydrogen bonded complex is shown.     

Discharge-flow/chemiluminescence and flash-photolysis/resonance fluorescence studies of the reaction O + SiH4 at room temperature

DF-CL studies using NO₂ chemiluminescence detection of O yielded a rate constant k₁ for O + SiH₄ of (2.6 ± 0.5)×10^?13 cm³ s^?1 at 295 K, where the 95% confidence interval reflects accuracy. FP-RF studies using flash photolysis of SO₂ followed by time-resolved vuv fluorescence detection of O at 295 K yielded k₁ = (3.0 ± 0.5) ×10^?13 cm³ s^?1. These results are in good accord with most previous measurements and lead to a combined best estimate of k₁ = (3.2 ± 0.4) × 10^?13 cm³ s^?1. The DF-CL and FP-RF methods appear to have little unrecognized systematic error. © 1993 John Wiley & Sons, Inc.     

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.     

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.     

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.     

Polarized fluorescence and rotational brownian motion

The equations governing the transient response of the emission anisotropy to a pulse of polarized light have been derived for macromolecules undergoing rotational diffusion.     

Excited state proton transfer reaction of two new intramolecularly hydrogen bonded Schiff bases at room temperature and 77K.

Two new orthohydroxy Schiff bases, 7-phenylsalicylidene benzylamine (PSBA) and 7-ethylsalicylideneaniline (ESA) have been synthesized. The excited state intramolecular proton transfer (ESIPT) and the structure of PSBA and ESA in its crystalline form and in the solvents n-hexane, n-heptane and 1,4-dioxane have been investigated by means of absorption, emission and nanosecond spectroscopy at room temperature and 77K. One ground state species has been detected both in neutral and basic solutions of both PSBA and ESA: the cis-enol form with an intramolecular hydrogen bond. The ESIPT and formation of keto tautomer are evidenced by a large Stokes shifted emission (approximately 12000 cm(-1)) at room temperature only in the case of ESA. On the other hand the keto tautomer is the predominant species at 77K in a solid matrix and as a solid sample at room temperature both in the case of ESA and PSBA. In the case of both ESA and PSBA the more intense, higher energy emission is due to the species which has not undergone ESIPT and attributed mainly due to cis-enol form. The trans-enol form is also observed by changing the excitation wavelength. Both the compounds are found to undergo a structural change to a zwitterionic and intermolecular hydrogen bonded form in the presence of a strong base like triethylamine. From the nanosecond measurements and quantum yield of fluorescence we have estimated the decay rates of proton transfer reaction in the case of PSBA. Our theoretical calculation at the AM1 level of approximation shows that the ground singlet state has a rather large activation barrier both in the case of PSBA and ESA. The barrier height is much lower on the corresponding excited singlet surface only in the case of ESA. The process is predicted to be endothermic in the ground state and exotherrmic in the excited singlet state.     

Designing tridentate ligands for ruthenium(II) complexes with prolonged room temperature luminescence lifetimes

Coordination complexes have been used extensively as the photoactive component of artificial photosynthetic devices. While polynuclear arrays increase the probability of light absorption, the incorporation of the stereogenic Ru(2,2'-bipyridine)(3)(2+) motif gives rise to diastereomeric mixtures whereas the achiral Ru(2,2':6',2"-terpyridine)(2)(2+) motif creates stereopure polynuclear complexes. Thus, polynuclear arrays composed of ruthenium(II) complexes of tridentate ligands are the targets of choice for light-harvesting devices. As Ru(II) complexes of tridentate ligands have short excited state lifetimes at room temperature (r. t.), considerable effort has been focused on trying to increase their r. t. luminescence lifetime for practical applications. This tutorial review will report on the sophisticated synthetic strategies currently in use to enhance the room temperature photophysical properties of Ru(II) complexes of tridentate ligands.     

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.     

Excess electron interactions with solvated DNA nucleotides: strand breaks possible at room temperature

When biological matter is subjected to ionizing radiation, a wealth of secondary low-energy (<20 eV) electrons are produced. These electrons propagate inelastically, losing energy to the medium until they reach energies low enough to localize in regions of high electron affinity. We have recently shown that in fully solvated DNA fragments, nucleobases are particularly attractive for such excess electrons. The next question is what is their longer-term effect on DNA. It has been advocated that they can lead to strand breaks by cleavage of the phosphodiester C(3')-O(3') bond. Here we present a first-principles study of free energy barriers for the cleavage of this bond in fully solvated nucleotides. We have found that except for dAMP, the barriers are on the order of 6 kcal/mol, suggesting that bond cleavage is a regular feature at 300 K. Such low barriers are possible only as a result of solvent and thermal fluctuations. These findings support the notion that low-energy electrons can indeed lead to strand breaks in DNA.     

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.     

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.