Search

Four new hetero- and homo-leptic iridium(III) bisterpyridine complexes have been prepared which incorporate aniline (tpy-φ-NH(2)), benzoic acid (tpy-φ-COOH), and benzyl alcohol (tpy-φ-CH(2)OH) substituents at the 4' positions of the tpy ligands (tpy = 2,2':6',2''-terpyridine, φ = phenylene). The electrochemical behaviour and ground and excited state spectroscopic properties of the complexes are reported, and the X-ray crystal structures of a homoleptic benzyl alcohol [Ir(tpy-φ-CH(2)OH)(2)](PF(6))(3), homoleptic aniline [Ir(tpy-φ-NH(2))(2)](PF(6))(3), and heteroleptic benzyl alcohol/aniline substituted complex [Ir(tpy-φ-CH(2)OH)(tpy-φ-NH(2))](PF(6))(3) have been solved. Complexes with aniline substituents were found to display absorption bands at around 430 nm corresponding to intraligand charge transfer (ILCT) that are sensitive to changes in solvent and pH. Strong emission in the visible region involving the ILCT state is observed in two of the complexes (Φ(e) = 0.7% and 2.6%) in acetonitrile. In the heteroleptic aniline/benzyl alcohol complex the Stokes shift is shown to be linearly related to solvent polarisability according to the Lippert equation, but only for solvents with weak hydrogen bonding interactions. Additionally, in water, emission from the ILCT state is quenched and only weak ligand centred (LC) emission is observed. The long lifetimes and quantum yields of these complexes make them interesting candidates for probes in sensing applications, especially [Ir(tpy-φ-CH(2)OH)(tpy-φ-NH(2))(2)](PF(6))(3) due to its unusual sensitivity to the solvent environment.

Conventional photochemical upconversion (UC) through homo-geneous triplet-triplet annihilation (TTA) is subject to several enthalpic losses that limit the UC margin. Here, we address one of these losses: the triplet energy transfer (TET) from the sensitizer to the emitter molecules. Usually, the triplet energy level of the emitter is set below that of the sensitizer. In our system, the triplet energy level of the emitter exceeds that of the sensitizer by ∼600 cm(-1). Choosing suitable concentrations for the sensitizer and emitter molecules, we can exploit entropy as a driving force for the migration of triplet excitation from the sensitizer to the emitter manifolds. Thereby we obtain a new record for the peak-to-peak TTA-UC energy margin of 0.94 eV. A modified Stern-Volmer analysis yields a TET rate constant of 2.0 × 10(7) M(-1) s(-1). Despite being relatively inefficient, the upconverted fluorescence is easily visible to the naked eye with irradiation intensities as low as 2 W cm(-2).

Luminescent solar concentrators promise to reduce the cost of solar energy, but are hindered by a number of losses. Escape of luminescence through the large waveguide-air interfaces can be attenuated through alignment of the optical transition dipole of the luminophore along the waveguide surface normal, directing the maximum possible proportion of luminescence into waveguide modes. We demonstrate such alignment using a guest-host dye-doped liquid crystal sandwiched between conductive glass slides. Application of a potential while illuminating through a narrow edge caused a drop in the intensity of luminescence escaping the large surfaces, and an increase in the intensity of light escaping the narrow edges of the system. This is explained in terms of alignment of the transition dipoles of the dye. We discuss implementation in a luminescent solar concentrator.

Photochemical upconversion is performed, whereby emitter triplet states are produced through triplet energy transfer from sensitizer molecules excited with low energy photons. The triplet emitter molecules undergo triplet-triplet annihilation to yield excited singlet states which emit upconverted fluorescence. Experiments comparing the 560 nm prompt fluorescence when rubrene emitter molecules are excited directly, using 525 nm laser pulses, to the delayed, upconverted fluorescence when the porphyrin sensitizer molecules are excited with 670 nm laser pulses reveal annihilation efficiencies to produce excited singlet emitters in excess of 20%. Conservative measurements reveal a 25% annihilation efficiency, while a direct comparison between the prompt and delayed fluorescence yield suggests a value as high as 33%. Due to fluorescence quenching, the photon upconversion efficiencies are lower, at 16%.

The electronic spectrum of the jet-cooled 1-indanyl radical has been identified in the products of a hydrocarbon discharge in argon. Electronic excitation spectra were observed in the region 20800-22600 cm(-1) by resonant two-color two-photon ionization and laser-induced fluorescence spectroscopies. In addition to the new spectrum at m/z = 117, the spectrum of 1-phenylpropargyl was also observed strongly, as was an unidentified spectrum carried by m/z = 133. The origin band of the 1-indanyl A2A''-X2A'' band system was observed at 21159 cm(-1) with the ionization potential of the radical experimentally determined to be 6.578 +/- 0.001 eV from a photoionization efficiency spectrum. Single vibronic level fluorescence was dispersed to determine the ground state vibrational frequencies that were utilized to confirm the identity of the radical in comparison with quantum chemical calculations. The calculated ground state frequencies and ionization potential, along with a calculated dispersed fluorescence spectrum of the origin band for the 1-indanyl radical, all provide a positive chemical identification.

The cis-1-vinylpropargyl (cis-1VPR, cis-pent-4-en-1-yn-3-yl) and trans-1-vinylpropargyl (trans-1VPR, trans-pent-4-en-1-yn-3-yl) radicals, produced in a supersonically cooled hydrocarbon discharge, have been identified by a synergy of 2-dimensional fluorescence and ionization spectroscopies, revealing their electronic origin transitions at 21,232 and 21,645 cm(-1) respectively. These assignments are supported by an excellent agreement between calculated ground state frequencies of cis-1VPR and trans-1VPR with those obtained by dispersed fluorescence spectroscopy. In addition, high-resolution rotational contours of the two bands are well simulated using calculated X- and A-state trans-1VPR and cis-1VPR rotational constants. Finally, computed origin transition energies of these two isomers are within several hundred wavenumbers of the observed band positions. With the 1-phenylpropargyl radical, the 1VPR isomers are the second 1-substituted propargyl species to have been observed abundantly from a hydrocarbon discharge, while no 3-substituted analogue has been positively identified. This is likely due to the greater resonance stabilization energy of the 1-substituted species, arising from concerted delocalization of the unpaired electron over the vinyl and propargyl moieties.

A new band system of C(2), e (3)Pi(g)-c (3)Sigma(u)(+) was studied by ab initio quantum chemical and experimental methods. The calculations were carried out at the multireference configuration interaction level of theory with Davidson's correction using aug-cc-pV6Z basis set and include core and core-valence correlation as well as relativistic corrections computed with aug-cc-pCVQZ and cc-pVQZ bases, respectively. The vibrational energies and rotational constants of the upper e (3)Pi(g) state were calculated from the computed ab initio potential energy curve. The ab initio results indicate that the electronic transition moment of the e (3)Pi(g)-c (3)Sigma(u)(+) system is approximately one-half that of the Fox-Herzberg e (3)Pi(g)-a (3)Pi(u) system. Franck-Condon factors were calculated for both systems and used to guide experiments aimed at discovering the e (3)Pi(g)-c (3)Sigma(u)(+) system. The e (3)Pi(g)(v(') = 4)-c (3)Sigma(u)(+)(v(") = 3) band of jet-cooled C(2) was successfully observed by laser-induced fluorescence spectroscopy by monitoring the ensuing e (3)Pi(g)-a (3)Pi(u) emission.

Infrared vibrational transition intensities of polycyclic aromatic hydrocarbons are known to depend strongly on the charge state. The detailed understanding of this effect for the C-H stretching modes has been approached by applying the quantum theory of atoms in molecules. Several benchmark calculations were undertaken in order to disentangle charge and size effects, from benzene (C(6)H(6)) up to the ovalene (C(32)H(14)) molecule. Upon decomposition of the dipole moment derivative along a C-H stretch into charge, charge flux, and dipole flux terms, it is found that it is the competition between the sum of the first two terms and the latter which drives the intensity, due to their opposing signs. Additionally, while the dipole flux term changes very little with size and charge, the other terms are strongly sensitive to these. This effect leads to a very weak C-H stretch intensity for cation sizes close to pyrene (C(16)H(10)) and comparable intensities between neutral and cations for the much larger ones. The astrophysical implications are discussed.

The D(1)((2)A("))-D(0)((2)A(")) electronic transition of the resonance-stabilized 1-phenylpropargyl radical, produced in a jet-cooled discharge of 3-phenyl-1-propyne, has been investigated in detail by laser-induced fluorescence excitation and dispersed single vibronic level fluorescence (SVLF) spectroscopy.The transition is dominated by the origin band at 21,007 cm(-1), with weaker Franck-Condon activity observed in a(') fundamentals and even overtones and combinations of a(") symmetry. Ab initio and density functional theory calculations of the D(0) and D(1) geometries and frequencies were performed to support and guide the experimental assignments throughout. Analysis of SVLF spectra from 16 D(1) vibronic levels has led to the assignment of 15 fundamental frequencies in the excited state and 19 fundamental frequencies in the ground state; assignments for many more normal modes not probed directly by fluorescence spectroscopy are also suggested. Duschinsky mixing, in which the excited state normal modes are rotated with respect to the ground state modes, is prevalent throughout, in vibrations of both a(') and a(") symmetry.

Gas-phase laser excitation spectra of the jet-cooled CCS radical were observed for the 2 (3)Sigma(-)-X (3)Sigma(-) electronic transition in a discharge of a gas mixture containing acetylene and H(2)S in Ar. The observed excitation spectra show complicated rotational structures, consisting of a much larger number of rotational lines than those expected for this size of linear molecule. The excited vibronic levels emit fluorescence, the lifetime of which is much longer than that estimated theoretically, indicating that the upper levels are strongly mixed with many "dark" background levels. Dispersed fluorescence spectra from single vibrational levels of the 2 (3)Sigma(-) state show long progressions of the C-S stretching mode, enabling observations of many vibrational levels in the ground electronic state.

We report studies aimed at unraveling the complicated structure of the CCl 2 A (1)B 1 <-- X (1)A 1 system. We have remeasured the fluorescence excitation spectrum from approximately 17,500 to 24,000 cm (-1) and report the term energies and A rotational constants of many new bands for both major isotopologues (C (35)Cl 2, C (35)Cl (37)Cl). We fit the observed term energies to a polyad effective Hamiltonian model and demonstrate that a single resonance term accounts for much of the observed mixing, which begins approximately 1300 cm (-1) above the vibrationless level of the A (1)B 1 state. The derived A (1)B 1 vibrational parameters are in excellent agreement with ab initio predictions, and the mixing coefficients deduced from the polyad model fit are in close agreement with those derived from direct fits of single vibronic level (SVL) emission intensities. The approach to linearity and thus the Renner-Teller (RT) intersection is probed through the energy dependence of the A rotational constant and fluorescence lifetime measurements, which indicate a barrier height above the vibrationless level of the X (1)A 1 state of approximately 23,000-23,500 cm (-1), in excellent agreement with ab initio theory.

The gas-phase laser-induced fluorescence (LIF) spectrum of a 1-phenylpropargyl radical has been identified in the region 20,800-22,000 cm(-1) in a free jet. The radical was produced from discharges of hydrocarbons including benzene. Disregarding C2, C3, and CH, this radical appears as the most strongly fluorescing product in a visible wavelength two-dimensional fluorescence excitation-emission spectrum of a jet-cooled benzene discharge. The structure of the carrier was elucidated by measurement of a matching resonant two-color two-photon ionization spectrum at m/z = 115 and density functional theory. The assignment was proven conclusively by observation of the same excitation spectrum from a low-current discharge of 3-phenyl-1-propyne. The apparent great abundance of the 1-phenylpropargyl radical in discharges of benzene and, more importantly, 1-hexyne may further underpin the proposed importance of the propargyl radical in the formation of complex hydrocarbons in combustion and circumstellar environments.

Ab initio oscillator strengths and lifetimes for the D (1)Sigma(u) (+)<--X (1)Sigma(g) (+) Mulliken system of C(2) are reported. The calculations were carried out at the MRCI level of theory with Davidson's correction using aug-cc-pV6Z basis sets and include core and core-valence correlation as well as relativistic corrections, computed with aug-cc-pCVQZ and cc-pVQZ bases, respectively. The MRCI calculations of transition moments utilize a biorthogonal transformation of the CASSCF orbitals. This approach was also employed to recompute the transition moments of the Swan, Ballik-Ramsay, Phillips, and d (3)Pi(g)<--c (3)Sigma(u) (+) systems of C(2), which were the subject of our previous study [D. L. Kokkin et al., J. Chem. Phys. 126, 084302 (2007)], resulting in an improved set of oscillator strengths for the latter systems as well. The oscillator strength of the Mulliken origin band, f(00) (DA), was calculated to be 0.0535, in excellent agreement with the accepted astronomical value of 0.054.

A two-dimensional fluorescence (excitation/emission) spectrum of C2 produced in an acetylene discharge was used to identify and separate emission bands from the d (3)Pi(g)<--c (3)Sigma(u) (+) and d (3)Pi(g)<--a (3)Pi(u) excitations. Rotationally resolved excitation spectra of the (4<--1), (5<--1), (5<--2), and (7<--3) bands in the d (3)Pi(g)<--c (3)Sigma(u) (+) system of C2 were observed by laser-induced fluorescence spectroscopy. The molecular constants of each vibrational level, determined from rotational analysis, were used to calculate the spectroscopic constants of the c (3)Sigma(u) (+) state. The principal molecular constants for the c (3)Sigma(u) (+) state are B(e)=1.9319(19) cm(-1), alpha(e)=0.018 55(69) cm(-1), omega(e)=2061.9 cm(-1), omega(e)x(e)=14.84 cm(-1), and T(0)(c-a)=8662.925(3) cm(-1). We report also the first experimental observations of dispersed fluorescence from the d (3)Pi(g) state to the c (3)Sigma(u) (+) state, namely, d (3)Pi(g)(v=3)-->c (3)Sigma(u) (+)(v=0,1).

A detailed study of the S1((1)B2)-S0((1)A1) electronic transition of jet-cooled fluorobenzene has been carried out using laser-induced fluorescence and dispersed fluorescence (DF) spectroscopies. Analysis of over 40 single vibronic level DF spectra resulted in the assignment of 16 fundamental frequencies in the excited electronic state. Progressions in totally symmetric modes, particularly in the ring-breathing mode nu9, feature in both types of fluorescence spectrum. There is also significant activity in non-totally-symmetric modes, with activity in Franck-Condon (FC)-allowed overtones, FC-forbidden combinations induced by Duschinsky mixing, and symmetry-forbidden transitions induced by the same Herzberg-Teller vibronic coupling mechanism that induces the benzene S1-S0 transition. Fermi resonances (FRs) are extensive throughout the spectrum, especially in the important FC-active a1 modes. A consequence of these extensive FRs is that several important previous assignments are shown to be incorrect and have been reassigned here. Ab initio and density functional theory calculations have also been performed to support the experimental assignments.

Excitation spectra of naphthalene dimer-argonn (n = 1-3) clusters are obtained by resonance enhanced multiphoton ionization time-of-flight mass spectroscopy. The spectra are generally independent of the number of attached argon atoms and reveal sharp structures which are fitted by superimposing independent monomer spectra. It is concluded that the rare-gas tagging technique reveals the presence of a T-shaped naphthalene dimer chromophore in the molecular beam.

The laser-induced fluorescence spectrum of 3-vinyl-1H-indene was recorded between 33,000 and 33,800 cm(-1). An origin band was observed at 33,455 cm(-1) along with several low-frequency modes. With the aid of density functional theory and configuration interaction calculations, the electronic transition was assigned as S1 <-- S0 and the short progression in an 80 cm(-1) mode was identified as a vinyl group torsion. Theoretical, spectroscopic, and thermochemical considerations suggest that the 3-vinyl-1H-indene spectrum results from excitation from both conformational isomers with the vinyl and indene double bonds in trans and cis arrangements. The results are discussed in the context of the identification of species arising from the discharge of benzene in argon.

The jet-cooled laser-induced fluorescence and dispersed fluorescence spectra of the S1(A1')<--S0(A1') transition of triphenylene are reported. The spectra exhibit false origins of e' symmetry which are modeled by performing calculations of Herzberg-Teller coupling using time-dependent density functional theory. It is found that this level of theory reproduces the main features of the observed spectra. The oscillator strength of the strongest band is calculated to be f=7x10(-4). From a combination of theory and the observed upper state lifetime of 41 ns, an estimate of the fluorescence yield is made of PhiF=0.084, in agreement with previous studies in the condensed phase.

High level ab initio calculations, using multireference configuration interaction (MRCI) techniques, have been carried out to investigate the spectroscopic properties of the singlet A 1Piu<--X 1Sigmag+ Phillips, the triplet d 3Pig<--a 3Sigmau Swan, the b 3Sigmag-<--a 3Piu Ballik-Ramsay, and the d 3Pig<--c 3Sigmau+ transitions of C2. The MRCI expansions are based on full-valence complete active space self-consistent-field reference states and utilize the aug-cc-pV6Z basis set to resolve valence electron correlation. Core and core-valence correlations and scalar relativistic energy corrections were also incorporated in the computed potential energy surfaces. Nonadiabatic and spin-orbit effects were explored and found to be of negligible importance in the calculations. Harmonic frequencies and rotational constants are typically within 0.1% of experiment. The calculated radiative lifetimes compare very well with the available experimental data. Oscillator strengths are reported for all systems: fv'v", where 0

We report the first observation of the predissociative B state of a halocarbene molecule. Rovibronic energy levels were measured in the B(1A') state of CHF by fluorescence dip detected optical-optical double resonance spectroscopy via the A state. The origin was found to lie 30 817.4 cm-1 above the zero point level of the X state. Rotational transitions within six purely bending states, and states involving one or two quanta of CF-stretch were observed, including the vibrational angular momentum components. Interpretation of the spectrum, with support of ab initio calculations, shows that CHF is quasilinear in the B state with a small (-200 cm-1) barrier to linearity which lies below the zero-point level. The rotational constant, B=1.04 to 1.09 cm-1, depending on vibrational state, again in good agreement with theory. All observed B state levels were predissociative, as evidenced by Lorentzian line broadening. Linewidths varied with initial state from 0.7-10.8 cm-1, corresponding to excited state lifetimes of 0.5-8 ps.

A new band system of C(2), d (3)Pi(g)<--c (3)Sigma(u) (+) is observed by laser induced fluorescence spectroscopy, constituting the first direct detection of the c (3)Sigma(u) (+) state of C(2). Observations were made by laser excitation of c (3)Sigma(u) (+)(v(")=0) C(2), produced in an acetylene discharge, to the d (3)Pi(g)(v(')=3) level, followed by detection of Swan band fluorescence. Rotational analysis of this band yielded rotational constants for the c (3)Sigma(u) (+)(v(")=0) state: B(0)=1.9218(2) cm(-1), lambda(0)=-0.335(4) cm(-1) and gamma(0)=0.011(2) cm(-1). The vibrational band origin was determined to be nu(3-0)=15861.28 cm(-1).

We report a new application of fluorescence spectroscopy for the identification and characterization of chemical species in complex environments. Simultaneous collection of a dispersed fluorescence spectrum for every step of the laser wavelength results in a two-dimensional spectrum of emission versus excitation wavelengths. This two-dimensional fluorescence (2DF) spectrum yields quick and intuitive assignments of a multitude of peaks in the separate fluorescence excitation and dispersed fluorescence spectra as belonging to the same species. We demonstrate the technique with the measurement of 2DF spectra of a discharge of dilute benzene into a supersonic free jet. A multitude of rovibronic bands due to the C(2) Swan and C(3) comet bands are immediately apparent and even unreported bands can be assigned intuituvely. Custom software filters are employed to enhance or reject emission from one or the other carrier to obtain excitation spectra arising from purely one carrier, or even a specific spectral component of a single carrier. The very characteristic 2DF fingerprints of C(2) and C(3) permit identification of another unidentified species in the discharge that absorbs at 476 nm, coincident with one of the diffuse interstellar bands.

A high-resolution single vibronic level emission study from the A (2)Pi(32) state of the HC(4)S radical is reported. Ground state density functional theory frequencies have been used to assign ground state vibronic levels involving three stretching modes nu(2), nu(3), and nu(5) in the region of 0-3250 cm(-1), while the frequency of nu(4) remains speculative. Tentative assignments are given for the complicated structures arising from Renner-Teller and spin-orbit interactions within the bending energy levels. From analysis of the dispersed emission spectra, Fermi resonances involving pairs of bands have been identified in the A (2)Pi(32)<--X (2)Pi(32) laser induced fluorescence spectrum.

The electronic excited-state properties of a series of dehydrogenated polycyclic aromatic hydrocarbons from phenyl through to decacyl are reported. The radicals were investigated by use of time-dependent density functional theory in conjunction with the B3LYP functional. The pi and n orbitals were seen to converge in energy as the system increased in size, yet all radicals were found to have A' ground states. In addition to the study of the electronic state symmetries, the excited-state transitions and oscillator strengths were investigated with the resulting transitions found within the visible region of the spectrum, placing these radicals in the large group of candidate carriers of the diffuse interstellar bands.

Expression of the neuropeptide calcitonin gene-related peptide (CGRP) in trigeminal ganglion is implicated in neurovascular headaches and temporomandibular joint disorders. Elevation of cytokines contributes to the pathology of these diseases. However, a connection between cytokines and CGRP gene expression in trigeminal ganglion nerves has not been established. We have focused on the effects of the cytokine tumor necrosis factor-alpha (TNF-alpha). TNFR1 receptors were found on the majority of CGRP-containing rat trigeminal ganglion neurons. Treatment of cultures with TNF-alpha stimulated CGRP secretion. In addition, the intracellular signaling intermediate from the TNFR1 receptor, ceramide, caused a similar increase in CGRP release. TNF-alpha caused a coordinate increase in CGRP promoter activity. TNF-alpha treatment activated the transcription factor NF-kappaB, as well as the Jun N-terminal kinase (JNK) and p38 mitogen-activated protein (MAP) kinase pathways. The importance of TNF-alpha induction of MAP kinase pathways was demonstrated by inhibiting MAP kinases with pharmacological reagents and gene transfer with an adenoviral vector encoding MAP kinase phosphatase-1 (MKP-1). We propose that selective and regulated inhibition of MAP kinases in trigeminal neurons may be therapeutically beneficial for inflammatory disorders involving elevated CGRP levels.

An 18-bp enhancer controls cell-specific expression of the calcitonin/calcitonin gene-related peptide gene. The enhancer is bound by a heterodimer of the bHLH-Zip protein USF-1 and -2 and a cell-specific factor from thyroid C cell lines. In this report we have identified the cell-specific factor as the forkhead protein Foxa2 (previously HNF-3beta). Binding of Foxa2 to the 18-bp enhancer was demonstrated using electrophoretic mobility shift assays. The cell-specific DNA-protein complex was selectively competed by a series of Foxa2 DNA binding sites, and the addition of Foxa2 antiserum supershifted the complex. Likewise, a complex similar to that seen with extracts from thyroid C cell lines was generated using an extract from heterologous cells expressing recombinant Foxa2. Interestingly, overexpression of Foxa2 activated the 18-bp enhancer in heterologous cells but only in the presence of the adjacent helix-loop-helix motif. Likewise, coexpression of USF proteins with Foxa2 yielded greater activation than by Foxa2 alone. Unexpectedly, Foxa2 overexpression repressed activity in the CA77 thyroid C cell line, suggesting that Foxa2 may interact with additional cofactors. The stimulatory role of Foxa2 at the calcitonin/calcitonin gene-related peptide gene enhancer was confirmed by short interfering RNA-mediated knockdown of Foxa2. As seen with Foxa2 overexpression, the effect of Foxa2 knockdown also required the adjacent helix-loop-helix motif. These results provide the first evidence for combinatorial control of gene expression by bHLH-Zip and forkhead proteins.

Antipsychotic drugs regulate gene transcription in striatal neurons by blocking dopamine D2-like receptors. Little is known about the underlying changes in chromatin structure, including covalent modifications at histone N-terminal tails that are epigenetic regulators of gene expression. We show that treatment with D2-like antagonists rapidly induces the phosphorylation of histone H3 at serine 10 and the acetylation of H3-lysine 14 in bulk chromatin from striatum and in nuclei of striatal neurons. We find that, in vivo, D2-like antagonist-induced H3 phospho-acetylation is inhibited by the NMDA receptor antagonist MK-801 and by the protein kinase A (PKA) inhibitor Rp-adenosine 3c',5c'-cyclic monophosphorothioate triethylammonium salt but increased by the PKA activator Sp-adenosine 3c',5c'-cyclic monophosphorothioate triethylammonium salt. Furthermore, in dissociated striatal cultures which lack midbrain and cortical pre-synaptic inputs, H3 phospho-acetylation was induced by glutamate, L-type Ca2+ channel agonists and activators of cAMP-dependent PKA but inhibited by NMDA receptor antagonists or PKA antagonists. The dual modification, H3pS10-acK14, was enriched at genomic sites with active transcription and showed the kinetics of the early response. Together, these results suggest that histone modifications and chromatin structure in striatal neurons are dynamically regulated by dopaminergic and glutamatergic inputs converging on the cellular level. Blockade of D2-like receptors induces H3 phospho-acetylation, H3pS10-acK14, through cAMP-dependent PKA, and post-synaptic NMDA receptor signaling., (Copyright 2004 International Society for Neurochemistry)

We report on the dynamics of multiphoton excitation and dissociation of NO(2) at wavelengths between 395 and 420 nm and intensities between 4 and 10 TW cm(-2). The breakup of the molecule is monitored by NO A (2)Sigma(+)n(')=1,0-->X (2)Pi(r)n(")=0 fluorescence as a function of time delay between the driving field and a probe field which depletes the emission. It is found that generation of n(')=0 and 1 NO A (2)Sigma(+) results in different fluorescence modulation patterns due to the intense probe field. The dissociation dynamics are interpreted in terms of nuclear motions over light-induced potentials formed by coupling of NO(2) valence and Rydberg states to the applied field. Based on this model, it is argued that the time and intensity dependences of A (2)Sigma(+)n(')=0-->X (2)Pi(r)n(")=0 fluorescence are consistent with delayed generation of NO A (2)Sigma(+)n(')=0 via a light-induced bond-hardening brought about by the transient coupling of the dressed A (2)B(2) and Rydberg 3ssigma (2)Sigma(g) (+) states of the parent molecule. The increasingly prompt decay of A (2)Sigma(+)n(')=1-->X (2)Pi(r)n(")=0 fluorescence with increasing intensity, on the other hand, is consistent with a direct surface crossing between the X (2)A(1) and 3ssigma (2)Sigma(g) (+) dressed states to generate vibrationally excited products., ((c) 2004 American Institute of Physics)

Little has been written about infant botulism in the emergency medicine literature, despite increasing references in the pediatric journals. We describe three cases diagnosed at The Children's Hospital in Denver, Colorado, over an 8-month period. A review of the literature follows, to discuss the clinical manifestations, differential diagnosis, diagnostic workup and treatment of the disease.