Combined Monte Carlo and quantum mechanics study of the solvatochromism of phenol in water. The origin of the blue shift of the lowest pi-pi* transition

A combined and sequential use of Monte Carlo simulations and quantum mechanical calculations is made to analyze the spectral shift of the lowest pi-pi* transition of phenol in water. The solute polarization is included using electrostatic embedded calculations at the MP2/aug-cc-pVDZ level giving a dipole moment of 2.25 D, corresponding to an increase of 76% compared to the calculated gas-phase value. Using statistically uncorrelated configurations sampled from the MC simulation,first-principle size-extensive calculations are performed to obtain the solvatochromic shift. Analysis is then made of the origin of the blue shift. Results both at the optimized geometry and in room-temperature liquid water show that hydrogen bonds of water with phenol promote a red shift when phenol is the proton-donor and a blue shift when phenol is the proton-acceptor. In the case of the optimized clusters the calculated shifts are in very good agreement with results obtained from mass-selected free jet expansion experiments. In the liquid case the contribution of the solute-solvent hydrogen bonds partially cancels and the total shift obtained is dominated by the contribution of the outer solvent water molecules. Our best result, including both inner and outer water molecules, is 570 +/- 35 cm(-1), in very good agreement with the small experimental shift of 460 cm(-1) for the absorption maximum.

Onset of pi(0) Suppression Studied in Cu plus Cu Collisions at root s(NN)=22.4, 62.4, and 200 GeV

Neutral pion transverse momentum (p(T)) spectra at midrapidity (|y| less than or similar to 0.35) were measured in Cu + Cu collisions at root s(NN) = 22.4, 62.4, and 200 GeV. Relative to pi(0) yields in p + p collisions scaled by the number of inelastic nucleon-nucleon collisions (N(coll)) the pi(0) yields for p(T) greater than or similar to 2 GeV/c in central Cu + Cu collisions are suppressed at 62.4 and 200 GeV whereas an enhancement is observed at 22.4 GeV. A comparison with a jet-quenching model suggests that final state parton energy loss dominates in central Cu + Cu collisions at 62.4 and 200 GeV, while the enhancement at 22.4 GeV is consistent with nuclear modifications in the initial state alone.

Inclusive pi(0), eta, and direct photon production at high transverse momentum in p plus p and d plus Au collisions at root s(NN)=200 GeV

We report a measurement of high-p(T) inclusive pi(0), eta, and direct photon production in p + p and d + Au collisions at root s(NN) = 200 GeV at midrapidity (0 < eta < 1). Photons from the decay pi(0) -> gamma gamma were detected in the barrel electromagnetic calorimeter of the STAR experiment at the Relativistic Heavy Ion Collider. The eta -> gamma gamma decay was also observed and constituted the first eta measurement by STAR. The first direct photon cross-section measurement by STAR is also presented; the signal was extracted statistically by subtracting the pi(0), eta, and omega(782) decay background from the inclusive photon distribution observed in the calorimeter. The analysis is described in detail, and the results are found to be in good agreement with earlier measurements and with next-to-leading-order perturbative QCD calculations.

Spectra of identified high-p(T) pi(+/-) and p((p)over-bar ) in Cu + Cu collisions at root s(NN)=200 GeV

We report new results on identified (anti) proton and charged pion spectra at large transverse momenta (3 < p(T) < 10 GeV/c) from Cu + Cu collisions at root s(NN) = 200 GeV using the STAR detector at the Relativistic Heavy Ion Collider (RHIC). This study explores the system size dependence of two novel features observed at RHIC with heavy ions: the hadron suppression at high-p(T) and the anomalous baryon to meson enhancement at intermediate transverse momenta. Both phenomena could be attributed to the creation of a new form of QCD matter. The results presented here bridge the system size gap between the available pp and Au + Au data, and allow for a detailed exploration of the onset of the novel features. Comparative analysis of all available 200 GeV data indicates that the system size is a major factor determining both the magnitude of the hadron spectra suppression at large transverse momenta and the relative baryon to meson enhancement.

Observation of pi(+)pi(-)pi(+)pi(-) photoproduction in ultraperipheral heavy-ion collisions at root s(NN)=200 GeV at the STAR detector

We present a measurement of pi(+)pi(-)pi(+)pi(-) photonuclear production in ultraperipheral Au-Au collisions at root s(NN) = 200 GeV from the STAR experiment. The pi(+)pi(-)pi(+)pi(-) final states are observed at low transverse momentum and are accompanied by mutual nuclear excitation of the beam particles. The strong enhancement of the production cross section at low transverse momentum is consistent with coherent photoproduction. The pi(+)pi(-)pi(+)pi(-) invariant mass spectrum of the coherent events exhibits a broad peak around 1540 +/- 40 MeV/c(2) with a width of 570 +/- 60 MeV/c(2), in agreement with the photoproduction data for the rho(0)(1700). We do not observe a corresponding peak in the pi(+)pi(-) final state and measure an upper limit for the ratio of the branching fractions of the rho(0)(1700) to pi(+)pi(-) and pi(+)pi(-)pi(+)pi(-) of 2.5% at 90% confidence level. The ratio of rho(0)(1700) and rho(0)(770) coherent production cross sections is measured to be 13.4 +/- 0.8(stat.) +/- 4.4(syst.)%.

K/pi Fluctuations at Relativistic Energies

We report K/pi fluctuations from Au+Au collisions at s(NN)=19.6, 62.4, 130, and 200 GeV using the STAR detector at the Relativistic Heavy Ion Collider. K/pi fluctuations in central collisions show little dependence on incident energy and are on the same order as those from NA49 at the Super Proton Synchrotron in central Pb+Pb collisions at s(NN)=12.3 and 17.3 GeV. We report results for the collision centrality dependence of K/pi fluctuations and results for charge-separated fluctuations. We observe that the K/pi fluctuations scale with the charged particle multiplicity density.

Scalar resonances in a unitary pi pi S-wave model for D(+)->pi(+)pi(-)pi(+)

We propose a model for D(+)->pi(+)pi(-)pi(+) decays following experimental results which indicate that the two-pion interaction in the S wave is dominated by the scalar resonances f(0)(600)/sigma and f(0)(980). The weak decay amplitude for D(+)-> R pi(+), where R is a resonance that subsequently decays into pi(+)pi(-), is constructed in a factorization approach. In the S wave, we implement the strong decay R ->pi(+)pi(-) by means of a scalar form factor. This provides a unitary description of the pion-pion interaction in the entire kinematically allowed mass range m(pi pi)(2) from threshold to about 3 GeV(2). In order to reproduce the experimental Dalitz plot for D(+)->pi(+)pi(-)pi(+), we include contributions beyond the S wave. For the P wave, dominated by the rho(770)(0), we use a Breit-Wigner description. Higher waves are accounted for by using the usual isobar prescription for the f(2)(1270) and rho(1450)(0). The major achievement is a good reproduction of the experimental m(pi pi)(2) distribution, and of the partial as well as the total D(+)->pi(+)pi(-)pi(+) branching ratios. Our values are generally smaller than the experimental ones. We discuss this shortcoming and, as a by-product, we predict a value for the poorly known D ->sigma transition form factor at q(2)=m pi(2).

New Measurement of the pi(0) Radiative Decay Width

High precision measurements of the differential cross sections for pi(0) photoproduction at forward angles for two nuclei, (12)C and (208)Pb, have been performed for incident photon energies of 4.9-5.5 GeV to extract the pi(0) -> gamma gamma decay width. The experiment was done at Jefferson Lab using the Hall B photon tagger and a high-resolution multichannel calorimeter. The pi(0) -> gamma gamma decay width was extracted by fitting the measured cross sections using recently updated theoretical models for the process. The resulting value for the decay width is Gamma(pi(0) -> gamma gamma) = 7.82 +/- 0.14(stat) +/- 0.17(syst) eV. With the 2.8% total uncertainty, this result is a factor of 2.5 more precise than the current Particle Data Group average of this fundamental quantity, and it is consistent with current theoretical predictions.

Exploiting pi-acceptors for the determination of thyroid hormones (T3 and T4) using a single interface flow system

A fully automated methodology was developed for the determination of the thyroid hormones levothyroxine (T4) and liothyronine (T3). The proposed method exploits the formation of highly coloured charge-transfer (CT) complexes between these compounds, acting as electron donors, and pi-acceptors such as chloranilic acid (CIA) and 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ). For automation of the analytical procedure a simple, fast and versatile single interface flow system (SIFA)was implemented guaranteeing a simplified performance optimisation, low maintenance and a cost-effective operation. Moreover, the single reaction interface assured a convenient and straightforward approach for implementing job`s method of continuous variations used to establish the stoichiometry of the formed CT complexes. Linear calibration plots for levothyroxine and liothyronine concentrations ranging from 5.0 x 10(-5) to 2.5 x 10(-4) mol L(-1) and 1.0 x 10(-5) to 1.0 x 10(-4) mol L(-1), respectively, were obtained, with good precision (R.S.D. <4.6% and <3.9%) and with a determination frequency of 26 h(-1) for both drugs. The results obtained for pharmaceutical formulations were statistically comparable to the declared hormone amount with relative deviations lower than 2.1%. The accuracy was confirmed by carrying out recovery studies, which furnished recovery values ranging from 96.3% to 103.7% for levothyroxine and 100.1% for liothyronine. (C) 2009 Elsevier B.V. All rights reserved.

Novel blue emitters based on pi-conjugated block copolymers

A series of new phenyl-based conjugated copolymers has been synthesized and investigated by vibrational and photoluminescence spectroscopy (PL). The materials are: poly( 1,4-phenylene-alt-3,6-pyridazine) (COP-PIR), poly(9,9-dioctylfluorene)-co-quaterphenylene (COP-PPP) and poly[(1,4-phenylene-alt-3,6-pyridazine)-co-(1,4-phenylene-alt-9,9-dioctylfluorene)] (COP-PIR-FLUOR), with 3.5% of fluorene. COP-PPP and COP-PIR-FLUOR have high fluorescence quantum yields in solution. Infrared and Raman spectra were used to check the chemical structure of the compounds. The copolymers exhibit blue emission ranging front 2.8 to 3.6 eV when excited at E(exc)=4.13 eV. Stokes-shift Values were estimated on pristine samples in their condensed state from steady-state PL-emission and PL-excitation spectra. They suggest a difference in the torsional angle between the molecular configuration of the polymer blocks at the absorption and PL transitions and also in the photoexcitation diffusion. Additionally, the time-resolved PL of these materials has been investigated by using 100 fs laser pulses at E(exc)=4.64 eV and a streak camera. Results show very fast biexponential kinetics for the two fluorene-based polymers with decay times below 300 ps indicating both intramolecular, fast radiative recombination and migration of photogenerated electron-hole pairs. By contrast, the PL of COP-PIR is less intense and longer lived, indicating that excitons are confined to the chains in this polymer. (C) 2008 Elsevier B.V. All rights reserved.

Blockade of vascular smooth muscle cell proliferation and intimal thickening after balloon injury by the sulfated oligosaccharide PI-88: Phosphomannopentaose sulfate directly binds FGF-2, blocks cellular signaling, and inhibits proliferation

Percutaneous transluminal coronary angioplasty is a frequently used interventional technique to reopen arteries that have narrowed because of atherosclerosis. Restenosis, or renarrowing of the artery shortly after angioplasty, is a major limitation to the success of the procedure and is due mainly to smooth muscle cell accumulation in the artery wall at the site of balloon injury. In the present study, we demonstrate that the antiangiogenic sulfated oligosaccharide, PI-88, inhibits primary vascular smooth muscle cell proliferation and reduces intimal thickening 14 days after balloon angioplasty of rat and rabbit arteries. PI-88 reduced heparan sulfate content in the injured artery wall and prevented change in smooth muscle phenotype. However, the mechanism of PI-88 inhibition was not merely confined to the antiheparanase activity of this compound. PI-88 blocked extracellular signal-regulated kinase-1/2 (ERK1/2) activity within minutes of smooth muscle cell injury. It facilitated FGF-2 release from uninjured smooth muscle cells in vitro, and super-released FGF-2 after injury while inhibiting ERK1/2 activation. PI-88 inhibited the decrease in levels of FGF-2 protein in the rat artery wall within 8 minutes of injury. PI-88 also blocked injury-inducible ERK phosphorylation, without altering the clotting time in these animals. Optical biosensor studies revealed that PI-88 potently inhibited (K-i 10.3 nmol/L) the interaction of FGF-2 with heparan sulfate. These findings show for the first time the capacity of this sulfated oligosaccharide to directly bind FGF-2, block cellular signaling and proliferation in vitro, and inhibit injury-induced smooth muscle cell hyperplasia in two animal models. As such, this study demonstrates a new role for PI-88 as an inhibitor of intimal thickening after balloon angioplasty. The full text of this article is available online at http://www.circresaha.org.

Granulocyte-Colony Stimulating Factor (G-CSF) induces mechanical hyperalgesia via spinal activation of MAP kinases and PI(3)K in mice

Granulocyte-colony stimulating factor (G-CSF) is a current pharmacological approach to increase peripheral neutrophil counts after anti-tumor therapies. Pain is most relevant side effect of G-CSF in healthy volunteers and cancer patients. Therefore, the mechanisms of G-CSF-induced hyperalgesia were investigated focusing on the role of spinal mitogen-activated protein (MAP) kinases ERK (extracellular signal-regulated kinase). JNK (Jun N-terminal Kinase) and p38, and PI(3)K (phosphatidylinositol 3-kinase). G-CSF induced dose (30-300 ng/paw)-dependent mechanical hyperalgesia, which was inhibited by local post-treatment with morphine. This effect of morphine was reversed by naloxone (opioid receptor antagonist). Furthermore, G-CSF-induced hyperalgesia was inhibited in a dose-dependent manner by intrathecal pre-treatment with ERK (PD98059), JNK (SB600125), p38 (SB202190) or PI(3)K (wortmanin) inhibitors. The co-treatment with MAP kinase and PI(3)K inhibitors, at doses that were ineffective as single treatment, significantly inhibited G-CSF-induced hyperalgesia. Concluding, in addition to systemic opioids, peripheral opioids as well as spinal treatment with MAP kinases and PI(3)K inhibitors also reduce G-CSF-induced pain. (C) 2011 Elsevier Inc. All rights reserved.

Impact of PI and NNRTI HAART-based therapy on oral lesions of Brazilian HIV-infected patients

Background: The incidence of oral lesions related to human immunodeficiency virus (HIV) infection have been investigated after treatment with highly active antiretroviral therapy (HAART) including protease inhibitors (PI) but no data are available on the effect of non-nucleoside reverse transcriptase inhibitor (NNRTI)-based therapy on incidence of acquired immunodeficiency syndrome (AIDS) oral manifestations or impact of HAART on oral manifestations of HIV infection in Brazil. The aim of this study was to describe the effects of anti-HIV therapy on the incidence of oral lesions during 17 years of AIDS epidemics in a Brazilian population. Methods: From 1989 to 2006, we collected data from 1595 consecutive HIV patients at the Special Care Dentistry Center, Sao Paulo, Brazil. We compared the effect of PI- and NNRTI-based antiretroviral therapy (ARVT) on the annual incidence of Kaposi sarcoma (KS), oral candidiasis (OC) and hairy leukoplakia (HL). The chi-squared test was used to test the association between oral lesions and therapeutic regimen (P < 0.05). Results: None of patients on ARVT presented with KS. Patients who used (nucleoside reverse transcriptase inhibitors) NRTI + PI were 0.9 times as likely to present with HL as those who used NRTI + NNRTI. This finding, however, was not statistically significant (P = 0.5). The relative risk for OC was 0.8 in patients with PI-based HAART. The increased risk among those on PIs was statistically significant (P = 0.004). Conclusions: The superiority of NNRTI regimens in decreasing OC incidence is consistent with current therapeutic guidelines which recommend NNRTI-based therapy as the treatment of choice for initial ARVT.

O caso da arte gr??fica Waj??pi e o embate contra a explora????o comercial inadequada: limites e potencialidades das pol??ticas p??blicas de prote????o ao patrim??nio imaterial

O presente estudo tem por finalidade discutir os limites e potencialidades dos instrumentos de pol??ticas p??blicas de prote????o ao patrim??nio imaterial, ?? luz das experi??ncias constitu??das em um caso concreto, qual seja, o registro da arte Kusiwa. Em 2003, a arte Kusiwa dos Waj??pi, no Amap?? recebeu o reconhecimento como Obra-Prima do Patrim??nio Oral e Imaterial da Humanidade, conferido pela UNESCO, um ano ap??s ter sido inscrita no Livro das Formas de Express??o e ter sido registrada pelo IPHAN. Entretanto, apesar dessas a????es de salvaguarda, esse patrim??nio imaterial vem sendo reiteradamente violado por meio do abuso comercial do uso n??o autorizado dos grafismos. O fato de as formas de produ????o e circula????o de conhecimento entre os coletivos ind??genas envolverem rela????es espec??ficas, que n??o se limitam ??s propostas atualmente dispon??veis na legisla????o sobre propriedade intelectual, confere um aspecto desafiador sobre a tem??tica. A partir do recorrente ass??dio da comercializa????o do Kusiwa, come??ou a haver um aprendizado institucional por parte do IPHAN e de diversos outros atores, principalmente quanto aos questionamentos envolvendo o alcance jur??dico de prote????o do patrim??nio dos bens registrados. Por tudo isso, o registro da arte Kusiwa foi o resultado de um processo mais amplo de conquistas de direitos e constru????o de cidadania, e gerou efeitos importantes n??o apenas para assegurar a transmiss??o intergeracional do conjunto de conhecimentos da cultura Waj??pi, mas, principalmente, porque a salvaguarda desse patrim??nio configurou-se como instrumento estrat??gico para o fortalecimento de a????es e lutas sociais que buscam assegurar a garantia de direitos culturais e at?? mesmo de direitos humanos de maneira ampla