Observation of a core-excited dipole-bound state ∼1 eV above the electron detachment threshold in cryogenically cooled acetylacetonate.

Dipole-bound states in anions exist when a polar neutral core binds an electron in a diffuse orbital through charge-dipole interaction. Electronically excited polar neutral cores can also bind an electron in a diffuse orbital to form Core-Excited Dipole-Bound States (CE-DBSs), which are difficult to observe because they usually lie above the electron detachment threshold, leading to very short lifetimes and, thus, unstructured transitions. We report here the photodetachment spectroscopy of cryogenically cooled acetylacetonate anion (C5H7O2-) recorded by detecting the neutral radical produced upon photodetachment and the infrared spectroscopy in He-nanodroplets.

Biological properties of a novel solution based on silver nanoclusters for arresting dentin caries.

Objectives: To test the biological properties of a novel non-restorative treatment method for arresting dentin caries based on silver nanoclusters (AgNCls) synthesized in polymethacrylic acid (PMAA).

Methods: Synthesis of AgNCls was performed by photoreduction of AgNO in PMAA with 355 nm/wavelength light. AgNCls/PMAA was characterized by absorption/fluorescence spectroscopy and optical and atomic force microscopy.

Selective Tautomer Production and Cryogenic Ion Spectroscopy of Radical Cations: The Uracil and Thymine Cases.

The vibrational and electronic spectroscopy of the radical cations of two nucleobases (NB) (uracil and thymine) was studied by cryogenic ion photodissociation spectroscopy. The radical cations have been generated from the photodissociation of NB-Ag complexes. A charge transfer process from the NB to Ag governs the deactivation mechanism, leading to the formation of the radical cation without further tautomerization.

Understanding the active role of water in laboratory chamber studies of reactions of the OH radical with alcohols of atmospheric relevance.

In this work, we studied the reactions of three cyclic aliphatic alcohols with OH at room temperature, atmospheric pressure and different humidities in a Teflon reaction chamber. It was determined that the lower the solubility of the alcohol in water, the larger the effect of the humidity on the acceleration of the reaction. This experimental evidence allows suggesting that the acceleration is due to the reaction of the co-adsorbed reactants at the air-water interface of a thin water film deposited on the Teflon walls of the reaction chamber, instead of between co-reactants dissolved in the water film or due to gas phase catalysis as previously suggested.

Application of 20% silver nanoclusters in polymethacrylic acid on simulated dentin caries; its penetration depth and effect on surface hardness.

The aims of this study were: To evaluate the surface hardness of simulated dentin caries lesions treated with either silver nanoclusters (AgNCls) synthesized in polymethacrylic acid (PMAA) or 38% silver diammine fluoride (SDF), as well as observe the penetration of the treatment solutions into the simulated caries lesions. Dentin blocks 4 mm thick obtained from caries-free third molars were sectioned and then simulated caries lesions on the occlusal dentin surfaces were created. Each specimen (n = 8) was divided into four sections: (A) treated with 20% AgNCls/PMAA; (B) treated with SDF 38% (FAgamin, Tedequim, Cordoba, Argentina); (C) sound tooth protected by nail-varnish during artificial caries generation (positive control); and (D) artificial caries lesion without surface treatment (negative control).

Cryogenic IR and UV spectroscopy of isomer-selected cytosine radical cation.

Oxidation of the nucleobases is of great concern for the stability of DNA strands and is considered as a source of mutagenesis and cancer. However, precise spectroscopy data, in particular in their electronic excited states are scarce if not missing. We here report an original way to produce isomer-selected radical cations of DNA bases, exemplified in the case of cytosine, through the photodissociation of cold cytosine-silver (C-Ag) complex.

Color changes and shear bond strength to simulated caries lesions treated with a novel solution of 20% silver nanoclusters in polymethacrylic acid.

The aims of the study were: (1) To compare the staining effect on demineralized dentin simulating caries between silver nanoclusters (AgNCls) synthesized using polymethacrylic acid (PMAA) and silver diammine fluoride (SDF), and (2) to measure the shear bond strength (SBS) of a glass ionomer cement (GIC) to simulated caries lesions with and without the application of AgNCls/PMAA or SDF. Dentine blocks 4 mm thick from twenty-four non-carious third molars were sectioned and coated with nail varnish (Revlon, New York, USA). Simulated caries lesions on occlusal dentin surfaces were created (66 h in 0.

Photodetachment of Deprotonated R-Mandelic Acid: The Role of Proton Delocalization on the Radical Stability.

The photodetachment and stability of R-Mandelate, the deprotonated form of the R-Mandelic acid, was investigated by observing the neutral species issued from either simple photodetachment or dissociative photodetachment in a cold anions set-up. R-Mandalate has the possibility to form an intramolecular ionic hydrogen-bond between adjacent hydroxyl and carboxylate groups. The potential energy surface along the proton transfer (PT) coordinate between both groups (O …H … OCO) features a single local minima, with the proton localized on the O group (OH… OCO).

Inter- and Intramolecular Proton Transfer in an Isolated (Cytosine-Guanine)H Pair: Direct Evidence from IRMPD Spectroscopy.

The collision-induced dissociation of the protonated cytosine-guanine pair was studied using tandem mass spectrometry (MS) coupled to infrared multiple photon dissociation spectroscopy with the free electron laser at Orsay (CLIO) to determine the structure of the CH and GH ionic fragments. The results were rationalized with the help of electronic structure calculations at the density functional theory level with the B3LYP/6-311++G(3df,2p) method. Several tautomers of each fragment were identified for the first time, some of which were previously predicted by other authors.

Guanine Tautomerism in Ionic Complexes with Ag Investigated by IRMPD Spectroscopy and Mass Spectrometry.

In this paper, we present the IRMPD spectra of three ionic complexes between guanine (G) and silver (Ag): [GAg-HO], [GAgG] produced in the electrospray ionization source of the mass spectrometer, and [GAg] produced by collision induced dissociation of the [GAgG] complex. On the basis of the comparison of theoretically calculated IR spectra, we show that there are two isomers of each complex containing two different keto-amino (KA) tautomers of G (GKA(1,9) and GKA(1,7)). The observed isomers are the most stable structures in aqueous solution, and their experimentally estimated relative populations are in better agreement with the calculated relative populations in solution than in the gas phase, both at 298 K.

Infrared Multiple Photon Dissociation Spectroscopy of Protonated Cyameluric Acid.

The present study reports the first structural characterization of protonated cyameluric acid ([CA + H]) in the gas phase, which paves the way for prospective bottom-up research on the condensed-phase chemistry of CA in the protonated form. A number of [CA + H] keto-enol isomers can a priori be produced as a result of protonation at available N and O positions of precursor neutral CA tautomers, yet ab initio computations predict different reduced [CA + H] isomer populations dominating the solution and gas phases that are involved in the ion generation process (i.e.

On the Interaction between Deprotonated Cytosine [C ] and Ba : Infrared Multiphoton Spectroscopy and Dynamics.

Gas-phase interactions between Ba and deprotonated cytosine (C ) were studied in [C Ba] and [C BaC] complexes by IRMPD spectroscopy coupled to tandem mass-spectrometry in combination with DFT calculations. For the [C BaC] complex only one [C KAN1O-Ba-C ] isomer was found, although the presence of another structure cannot be excluded. This isomer features a central tetracoordinated Ba that simultaneously interacts with keto-amino [C ] deprotonated on N1 and neutral keto-amino C.

On the photophysics of electrochemically generated silver nanoclusters: spectroscopic and theoretical characterization.

Ligand-free atomic silver nanoclusters (AgNCs) were successfully synthesized following the electrochemical procedure developed by Lopez-Quintela and col. (D. Buceta, N.

Rate Coefficient and Mechanism of the OH-Initiated Degradation of 1-Chlorobutane: Atmospheric Implications.

In this work, we investigate the degradation process of 1-chlorobutane, initiated by OH radicals, under atmospheric conditions (air pressure of 750 Torr and 296 K) from both experimental and theoretical approaches. In the first one, a relative kinetic method was used to obtain the rate coefficient for this reaction, while the products were identified for the first time (1-chloro-2-butanone, 1-chloro-2-butanol, 4-chloro-2-butanone, 3-hydroxy-butanaldehyde, and 3-chloro-2-butanol) using mass spectrometry, allowing suggesting a reaction mechanism. The theoretical calculations, for the reactive process, were computed using the BHandHLYP/6-311++G(d,p) level of theory, and the energies for all of the stationary points were refined at the CCSD(T) level.

Photodetachment of deprotonated aromatic amino acids: stability of the dehydrogenated radical depends on the deprotonation site.

While aromatic amino acids in their deprotonated form have been well characterized by IR and photoelectron spectroscopies, no information is available on the neutral dehydrogenated radicals and, in particular, on their stability when the deprotonation site is changed. This is investigated by observing the neutral fragment issued from either simple photodetachment or dissociative photodetachment of the deprotonated aromatic amino acids phenylalanine, tyrosine, and tryptophan. We show that the dehydrogenated radicals of aromatic amino acids produced upon photodetachment of molecules deprotonated on the carbonyl group dissociate without barrier, leading to the formation of CO and a radical amine.

UV Photofragmentation of Cold Cytosine-M Complexes (M: Na, K, Ag).

The UV photofragmentation spectra of cold cytosine-M complexes (M: Na, K, Ag) were recorded and analyzed through comparison with geometry optimizations and frequency calculations of the ground and excited states at the SCS-CC2/Def2-SVPD level of theory. While in all complexes, the ground state minimum geometry is planar ( symmetry), the ππ* state minimum geometry has the NH group slightly twisted and an out-of-plane metal cation. This was confirmed by comparing the simulated ππ* Franck-Condon spectra with the vibrationally resolved photofragmentation spectra of CytNa and CytK.

Dissociative photodetachment vs. photodissociation of aromatic carboxylates: the benzoate and naphthoate anions.

The competition between dissociative photodetachment and photodissociation of cold benzoate and naphthoate anions was studied through measurement of the kinetic energy of the neutral fragments and intact parent benzoyloxy and naphtoyloxy radicals as well as by detecting the anionic fragments whenever they are produced. For the benzoate anion, there is no ionic photodissociation and the radical dissociation occurs near the vertical photodetachment energy. This is in agreement with DFT calculations showing that the dissociation energy in CO2 and C6H5˙ is very low.

Water catalysis of the reaction between hydroxyl radicals and linear saturated alcohols (ethanol and n-propanol) at 294 K.

The rate coefficients for the reactions of OH with ethanol and n-propanol were determined by a relative method in a smog chamber at 294 K, 1 atm of air or N2 and a wide range of humidity. The rate coefficients for both reactions show a quadratic dependence on the water concentration as in the case of the reaction of OH with methanol (Jara-Toro et al. Angew.

Solvation of barium atoms and singly charged cations in acetonitrile clusters.

The size distributions of neutral and cationic Ba (CHCN) ( = 0, +1; ≤ 7) clusters, as produced by a standard laser vaporization-supersonic expansion pick-up source, were determined from molecular beam experiments. The size distribution for cations is in the range of = 1-7, whereas only the = 1 complex is observed for neutral clusters, and these two features are unaffected by the variables controlling the performance of the cluster source. The distinct behavior is compatible with the expected charge-dipole interactions in the ionic species, which are stronger than the dipole induced-dipole interactions at play in neutral clusters, and it is corroborated by the relative magnitude of the theoretical successive binding energies (SBEs) for the lowest-lying isomers of cationic and neutral clusters with = 1-5, as computed at the density functional theory level.

Optical properties and charge distribution in rod-shape DNA-silver cluster emitters.

While the atomic structure of DNA_Agn clusters remains unknown many efforts have been made to understand the photophysical properties of this type of systems. It is known that partial oxidation of the silver cluster is necessary for generation of fluorescent emitters. In this sense, the rod-shape model proposed by Gwinn and coworkers (D.

Tautomerism and electronic spectroscopy of protonated 1- and 2-aminonaphthalene.

Experimental and theoretical investigations of the excited states of protonated 1- and 2-aminonaphthalene are presented. The electronic spectra are obtained by laser induced photofragmentation of the ions captured in a cold ion trap. Using ab initio calculations, the electronic spectra can be assigned to different tautomers which have the proton on the amino group or on the naphthalene moiety.

Fingerprints of Both Watson-Crick and Hoogsteen Isomers of the Isolated (Cytosine-Guanine)H Pair.

 Gas phase protonated guanine-cytosine (CGH) pair was generated using an electrospray ionization source from solutions at two different pH (5.8 and 3.2).

Excited State Dynamics of Cold Protonated Cytosine Tautomers: Characterization of Charge Transfer, Intersystem Crossing, and Internal Conversion Processes.

Charge transfer reactions are ubiquitous in chemical reactivity and often viewed as ultrafast processes. For DNA, femtochemistry has undeniably revealed the primary stage of the deactivation dynamics of the locally excited state following electronic excitation. We here demonstrate that the full time scale excited state dynamics can be followed up to milliseconds through an original pump-probe photodissociation scheme applied to cryogenic ion spectroscopy.

DNA-protected silver emitters: charge dependent switching of fluorescence.

The relationship between the state of charge and spectroscopy of DNA-protected silver emitters is not yet well understood. This remains one of the major issues to unveil in order to fully disentangle the spectroscopic features of these novel systems. It is a well known fact that a fluorescence response arises upon chemical reduction of silver cations attached to DNA, leading to neutral (or partially oxidized) "bright" clusters.

Water Catalysis of the Reaction between Methanol and OH at 294 K and the Atmospheric Implications.

The rate coefficient for the reaction CH OH+OH was determined by means of a relative method in a simulation chamber under quasi-real atmospheric conditions (294 K, 1 atm of air) and variable humidity or water concentration. Under these conditions, a quadratic dependence of the rate coefficient for the reaction CH OH+OH on the water concentration was found. Thus the catalytic effect of water is not only important at low temperatures, but also at room temperature.