Unraveling the dynamics of the C(3P,1D) + C2H2 reactions by the crossed molecular beam scattering technique

A detailed investigation of the dynamics of the reactions of ground- and excited-state carbon atoms, C(3P) and C(1D), with acetylene is reported over a wide collision energy range (3.6-49.1 kJ mol-1) using the crossed molecular beam (CMB) scattering technique with electron ionization mass spectrometric detection and time-of-flight (TOF) analysis. We have exploited the capability of (a) generating continuous intense supersonic beams of C(3P, 1D), (b) crossing the two reactant beams at different intersection angles (45, 90, and 135 degrees ) to attain a wide range of collision energies, and (c) tuning the energy of the ionizing electrons to low values (soft ionization) to suppress interferences from dissociative ionization processes. From angular and TOF distribution measurements of products at m/z=37 and 36, the primary reaction products of the C(3P) and C(1D) reactions with C2H2 have been identified to be cyclic (c)-C3H + H, linear (l)-C3H + H, and C3 + H2. From the data analysis, product angular and translational energy distributions in the center-of-mass (CM) system for both the linear and cyclic C3H isomers as well as the C3 product from C(3P) and for l/c-C3H and C3 from C(1D) have been derived as a function of collision energy from 3.6 to 49.1 kJ mol-1. The cyclic/linear C3H ratio and the C3/(C3 + c/l-C3H) branching ratios for the C(3P) reaction have been determined as a function of collision energy. The present findings have been compared with those from previous CMB studies using pulsed beams; here, a marked contrast is noted in the CM angular distributions for both C3H- and C3-forming channels from C(3P) and their trend with collision energy. Consequently, the interpretation of the reaction dynamics derived in the present work contradicts that previously proposed from the pulsed CMB studies. The results have been discussed in the light of the available theoretical information on the relevant triplet and singlet C3H2 ab initio potential energy surfaces (PESs). In particular, the branching ratios for the C(3P) + C2H2 reaction have been compared with the available theoretical predictions (approximate quantum scattering calculations and quasiclassical trajectory calculations on ab initio triplet PESs and, very recent, statistical calculations on ab initio triplet PESs as well as on ab initio triplet/singlet PESs including nonadiabatic effects, that is, intersystem crossing). While the experimental branching ratios have been corroborated by the statistical predictions, strong disagreement has been found with the results of the dynamical calculations. The astrophysical implications of the present results have been noted.     

Hyperpigmentation induced by topical 5-aminolaevulinic acid plus visible light

Photodynamic therapy (PDT) with 5-aminolaevulinic acid (ALA) is an alternative tool for the treatment of superficial non-melanoma skin cancers. Recently ALA-PDT has been employed with encouraging results also for warts, condylomata and psoriasis. In this study the effects of topical ALA plus irradiation with visible light on intact human skin have been evaluated. Five skin areas (A, B, C, D, and E) on the inner upper part of the arms of five healthy volunteers (skin types III and IV) were treated with (A) ALA 20% in base cream without irradiation, (B) only the vehicle (base cream) without ALA, (C, D and E) ALA cream at the concentrations of 5, 10 and 20%, respectively; all treatments were applied with an occlusive dressing. Four hours after ALA or vehicle application areas B, C, D and E were irradiated with a fixed dose of 40 J/cm(2). ALA penetration through the intact skin was evaluated by in vivo fluorescence determination. The effects on healthy skin were evaluated by clinical and chromometric examinations, light microscopy, immunohistochemistry and electron microscopy. RESULTS: (1) in vivo fluorescence demonstrated that ALA is able to penetrate through the intact skin, when applied with occlusive dressing and induces a classical fluorescence peak due to Protoporphyrin IX (PpIX) formation, which is the active photosensitiser. (2) Skin areas receiving ALA plus irradiation showed erythema and swelling just after the irradiative session and hyperpigmentation 48-72 h later. (3) Colourimetric data confirmed significant skin colour changes: values a* (representing the erythematous changes) increased only on the skin areas where ALA+irradiation were applied and during the 48 h after irradiation, thereafter a* began to decrease; values L* (pigmentation) increased during the 2 weeks following treatment. (4) Histopathological, immunohistochemical (S100, HMB-45) and electron microscopic findings showed an absolute increment of the number of melanocytes, which appeared clearly activated. In conclusion the application of ALA cream followed by irradiation is able to induce a pigmentation response in healthy human skin, at least in skin types III and IV. This melanocytic activation could have a potential for the treatment of skin disorders characterised by hypopigmentation.     

Hausdorff measures of subgroups of \mathbb{R }/\mathbb{Z } and \mathbb{R }

For a sequence $\underline{u}=(u_n)_{n\in \mathbb{N }}$ of integers, let $t_{\underline{u}}(\mathbb{T })$ be the group of all topologically $\underline{u}$ -torsion elements of the circle group $\mathbb{T }:=\mathbb{R }/\mathbb{Z }$ . We show that for any $s\in ]0,1[$ and $m\in \{0,+\infty \}$ there exists $\underline{u}$ such that $t_{\underline{u}}(\mathbb{T })$ has Hausdorff dimension $s$ and $s$ -dimensional Hausdorff measure equal to $m$ (no other values for $m$ are possible). More generally, for dimension functions $f,g$ with $f(t)\prec g(t), f(t)\prec \!\!\!\prec t$ and $g(t)\prec \!\!\!\prec t$ we find $\underline{u}$ such that $t_{\underline{u}}(\mathbb{T })$ has at the same time infinite $f$ -measure and null $g$ -measure.     

The deprotonation of benzyl alcohol radical cations: a mechanistic dichotomy in the gas phase as in solution

The gas-phase acidity of ionized benzyl alcohol and of some of its derivatives with selected reference bases has been studied by Fourier Transform Ion Cyclotron Resonance (FT-ICR) mass spectrometry. The aim was to relate the gas-phase reactivity to the behavior in aqueous solution of the radical cations of benzyl alcohols bearing methoxy substituent(s) on the phenyl ring which are known to undergo deprotonation at both the CH2 and OH groups. The dual reactivity behavior is confirmed in the gas phase, in which the prototypical ion, C6H5CH2OH*+, is deprotonated at both the CH2 and OH groups, whereas the ring hydrogens are not involved. An increasing extent of O-deprotonation is shown as the strength of the base increases. Appropriate methyl substitution, as in the radical cations of C6H5C(Me)2OH and C6H5CH2OMe, allows only O- or C-acidity. The two processes are characterized by comparable thermodynamic features with a Gas-phase Basicity (GB) value of 852 kJ mol(-1) for the cumyloxyl radical and 850 kJ mol(-1) for the alpha-methoxybenzyl radical. The possible origin of the observed mechanistic dichotomy is discussed.     

The first ruthenium-alkyne-dihydride reported is now recognized as an intermediate in the homogeneous hydrogenation of diphenylacetylene: Crystal structure of (μ-H)2Ru3(CO)9(μ3-η2-∥-C2Ph2)

The title complex (complex1) was the first alkyne-substituted triruthenium dihydrido cluster to be reported and was characterized by spectroscopy as a triangular cluster with the alkyne parallel to a Ru-Ru edge. Recently, we have found that1 is a key intermediate in the homogeneous hydrogenation of diphenylacetylene catalyzed by tetrahedral Ru₄ and FeRu₃ clusters. Since the discovery of1, a great number of complexes with alkynes parallel to a cluster edge have been reported; at present this is the more common bonding mode for alkynes on trinuclear clusters. The structural features of1 allow a comparison with those of other ruthenium-containing derivatives and help to draw suggestions of the role of1 in hydrogenation catalysis.     

Silica nanoparticles for fluorescence sensing of Zn(II): exploring the covalent strategy

Silica nanoparticles (about 15 nm diameters), which contain a derivative of 6-methoxy-8-(p-toluensulfonamido)-quinoline (TSQ) as a Zn(II) fluorescent probe covalently linked to the silica network, were prepared and studied as Zn(II) fluorescent chemosensors. The systems selectively detect Zn(II) ions in water rich solutions with a submicromolar sensitivity: 0.13 microM concentrations of Zn(II) can be measured with the only interference of Cu(II) and Cd(II) ions. Compared with free TSQ, the nanoparticles based systems have the advantage that they can be employed in aqueous solutions without aggregation problems while at the same time, they maintain a similar Zn(II) affinity and sensing ability. Addition of a second, substrate insensitive, fluorophore to the particles leads to the realization of a ratiometric sensor.     

Real‐Time Nanomicroscopy via Three‐Dimensional Single‐Particle Tracking

We developed a new method for real‐time, three‐dimensional tracking of fluorescent particles. The instrument is based on a laser‐scanning confocal microscope where the focus of the laser beam is scanned or orbited around the particle. Two confocal pinholes are used to simultaneously monitor regions immediately above and below the particle and a feedback loop is used to keep the orbit centered on the particle. For moderate count rates, this system can track particles with 15 nm spatial resolution in the lateral dimensions and 50 nm in the axial dimension at a temporal resolution of 32 ms. To investigate the interaction of the tracked particles with cellular components, we have combined our orbital tracking microscope with a dual‐color, wide‐field setup. Dual‐color fluorescence wide‐field images are recorded simultaneously in the same image plane as the particle being tracked. The functionality of the system was demonstrated by tracking fluorescent‐labeled artificial viruses in tubulin‐eGFP expressing HUH7 cells. The resulting trajectories can be used to investigate the microtubule network with super resolution.