The electronic properties of three popular high spin complexes [TM(acac)3, TM = Cr, Mn, and Fe] revisited: an experimental and theoretical study.

The occupied and unoccupied electronic structures of three high spin TM(acac)3 (TM = Cr, Mn, and Fe) complexes (I, II, and III, respectively) were studied by revisiting their literature vapour-phase He(i) and, when available, He(ii) photoemission (PE) spectra and by means of original near-edge X-ray absorption fine structure (NEXAFS) spectroscopic data recorded at the O K-edge (OK-edge) and TM L2,3-edges (TML2,3-edges). The assignments of the vapour-phase He(i)/He(ii) PE spectra were guided by the results of spin-unrestricted non-relativistic Slater transition state calculations, while the OK-edge and TML2,3-edge spectroscopic pieces of evidence were analysed by exploiting the results of spin-unrestricted scalar-relativistic time-dependent density functional theory (DFT) and DFT/ROCIS calculations, respectively. Although the actual symmetry (D3, in the absence of any Jahn-Teller distortion) of the title molecules allowed an extensive mixing between TM t2g-like and eg-like atomic orbitals, the use of the Nalewajski-Mrozek TM-O bond multiplicity index combined with a thorough analysis of the ground state (GS) outcomes allowed the assessment of the TM-O bond weakening associated with the progressive TM 3d-based eg-like orbital filling. The experimental information provided by OK-edge spectra was rather poor; nevertheless, the combined use of symmetry, orbitals and spectra allowed us (i) to rationalise minor differences characterizing spectral features along the series, (ii) to quantify the contribution provided by the ligand-to-metal-charge-transfer (LMCT) excitations to the different spectral features, and (iii) to recognize the t2g-/eg-like nature of the TM 3d-based orbitals involved in LMCT transitions. As far as the TML2,3-edge spectra and the DFT/ROCIS results were concerned, the lowest lying I,IIL3 spectral features included states having either the GS spin multiplicity (S(I) = 3/2, S(II) = 2) or, at higher excitation energies (EEs), states with ΔS = ±1. In contrast to that, only states with ΔS = 0, -1 significantly contributed to the IIIL3 spectral pattern. Along the whole series, the L3 higher EE side was systematically characterized by states involving TM2p → π4 MLCT excitations; as such, coupled-single excitations with ΔS = 0 were involved in I and II, while single MLCT TM2p → π4 transitions with ΔS = -1 were involved in III.

RT-PCR quantification of periodontal pathogens in crack users and non-users.

OBJECTIVE: To compare counts of Aggregatibacter actinomycetemcomitans, Prevotella intermedia, Porphyromonas gingivalis and Fusobacterium nucleatum between crack users and non-users. MATERIALS AND METHODS: A cross-sectional study was conducted involving seventy-four crack cocaine users and eighty-one non-users matched for age, gender and tobacco use. Demographic and clinical variables were analysed. Subgingival bacterial samples were collected from four sites with the greatest probing depths and were analysed using real-time polymerase chain reaction. RESULTS: No significant difference was found in the prevalence of total counts for each bacterial species analysed between groups. However, crack users had a 1.85 (95% CI: 1.03-3.31), 2.19 (95% CI 1.24-3.88), 2.53 (95% CI 1.27-5.04) and 2.40 (95% CI 1.22-4.75) greater probability of having the higher counts (≥75th percentile) for Aggregatibacter actinomycetemcomitans, Porphyromonas gingivalis, Prevotella intermedia and Fusobacterium nucleatum, respectively. CONCLUSION: Although some crack users had higher (>75th percentile) bacterial counts for Aggregatibacter actinomycetemcomitans, Porphyromonas gingivalis, Prevotella intermedia and Fusobacterium nucleatum, total counts did not differ between crack users and non-users, leading to the hypothesis that the higher occurrence of periodontitis on crack users may be related to other non-bacterial factors.

L2,3-edges absorption spectra of a 2D complex system: a theoretical modelling.

L2,3-edges absorption spectra of FePc (I) and FePc(η2-O2) (II) on Ag(110) have been modelled using the DFT/ROCIS method. Despite disregarding the presence of the substrate, the agreement between experiment and theory is remarkable. Moreover, theoretical results confirm the fraction of II (70%) present on the surface, thus allowing a thorough assignment of each experimental spectral feature. Ground state (GS) theoretical outcomes pertaining to I and II provide an intimate understanding of the electron transfer pathway ruling the I-based catalytic oxygen reduction reaction. DFT/ROCIS outcomes indicate that the lower excitation energy (EE) side of the I/IIL3 intensity distributions mainly includes states having the GS number of unpaired electrons (two in I and six in II), whereas states with higher/lower spin multiplicity contribute to the I/IIL3 higher EE side. The occurrence of states involving metal to ligand charge transfer transitions implying low lying empty π* ligand-based orbitals on the I/IIL3 higher EE sides have been confirmed.

A theoretical study of the L3 pre-edge XAS in Cu(II) complexes.

L2,3 spectra of Cu(II) complexes have been simulated by means of time dependent DFT. Besides the agreement between theory and experiment, the adopted approach provided further insights into the use of the Cu(II) L3-edge intensity and position to investigate the Cu-ligand symmetry-restricted covalency and the ligand-field strength.

Tuning the catalytic activity of Ag(110)-supported Fe phthalocyanine in the oxygen reduction reaction.

A careful choice of the surface coverage of iron phthalocyanine (FePc) on Ag (110) around the single monolayer allows us to drive with high precision both the long-range supramolecular arrangement and the local adsorption geometry of FePc molecules on the given surface. We show that this opens up the possibility of sharply switching the catalytic activity of FePc in the oxygen reduction reaction and contextual surface oxidation in a reproducible way. A comprehensive and detailed picture built on diverse experimental evidence from scanning tunnelling microscopy, X-ray photoelectron spectroscopy and X-ray absorption spectroscopy, coupled with density functional theory calculations, sheds new light on the nature of the catalytically active molecule-surface coordination and on the boundary conditions for its occurrence. The results are of relevance for the improvement of the catalytic efficiency of metallo-macrocycles as viable substitutes for platinum in the cathodic compartment of low-temperature fuel cells.

Superhydrophilic and tribological improvements of polymeric surfaces via plasma enhanced chemical vapor deposition ceramic coatings.

The main object of this study is the treatment of polymeric (PVC, PC) surfaces with the aim of inducing enhanced superhydrophilic characteristics together with nanohardness features; this would allow polymeric surfaces to have longer durability and prevent the accumulation of dirt on the surface which could disable the proper use of these polymeric surfaces. Indeed plastic surfaces are difficult substrates to be covered effectively and functionalized, mainly due to their high sensitivity to heat treatments and irradiation in the UV-Vis range together with their inert behavior. Their functionalization is achieved through the deposition of ceramic coatings such as titania (TiO2), on the polymeric surfaces via PECVD (Plasma Enhanced Chemical Vapor Deposition) at low temperatures. Characterizations are carried out by contact angle analysis for the superhydrophilic characteristics, and by nanoindentation analysis for the tribological features. A cold PECVD discontinuous method allowed us to improve nanohardness, reaching a value of 1.39 GPa which is nearly ten times higher than that of the uncoated polymeric substrate, and seems a promising solution for improving uniformity of the coatings. Superhydrophilic behavior of the activated TiO2 surfaces showed contact angle values lower than 10 degrees.

STM investigation of temperature-dependent two-dimensional supramolecular architectures of C60 and amino-tetraphenylporphyrin on Ag(110).

Multicomponent supramolecular self-assemblies of exceptional long-range order and low defectivity are obtained if C(60) and 5-(4-aminophenyl)-10,15,20-triphenylporphyrin (TPP-NH2) are assembled on Ag(110) by sequential evaporation in the submonolayer range of TPP-NH2 and fullerene on the substrate surface and subsequent annealing. A (+/-2 -3, 6 +/- 3) array consisting of supramolecular stripes of a 1:1 C(60)/TPP-NH2 2D adduct develops at 410 K (the low temperature, LT, phase). If the LT phase is annealed at 470 K, then a 3:1 fullerene/TPP-NH2 (+/-3 -5, 5 +/- 5) nanoporous array (the HT phase) forms, with each pore containing a single porphyrin molecule. Phase separation occurs by annealing the HT phase at 520 K. Structural models are proposed and discussed on the basis of the experimental scanning tunneling microscopy results.

Theoretical study of the chemisorption of CO on Al2O3(0001).

Density functional molecular cluster calculations have been used to study the adsorption of CO on the alpha-Al2O3-(0001) surface. Substrate and adsorbate geometry modifications, adsorption enthalpies, and adsorbate vibrations are computed. Despite the rather small size of the employed cluster, relaxation phenomena evaluated for the clean surface agree well with experimental measurements and periodic slab calculations and mainly consist of an inward relaxation of the Lewis acid site (Lsa). Different adsorbate arrangements, perpendicular and parallel to the surface, have been considered. Among them, the most state CO chemisorption geometry (delta Hads approximately -13 kcal/mol) is that corresponding to the adsorbate perpendicular to the surface, atop Lsa and C-down oriented. The C-O stretching frequency (nu C-O) computed for such an arrangement is 2158 cm-1, i.e., blue shifted by 44 cm-1 with respect to the free adsorbate. The lack of experimental evidence pertaining to CO interacting with a well-defined alpha-Al2O3(0001) surface prevents the possibility of a direct check of the computed quantities. Nevertheless, low-temperature IR data for CO on alumina powders (Zecchina, A.; Escalona Platero, E.; Otero Areán, C. J. Catal. 1987, 107, 244) indicate for the chemisorbed species a delta nu = 12 cm-1. The adsorbate-substrate interaction relieves some of the Lsa relaxation, even if the Lsa electronic structure is only slightly affected upon chemisorption.

Comparative evaluation of the haemodynamic effects of continuous negative external pressure (CNEP) and positive end-expiratory pressure (PEEP) in mechanically ventilated trauma patients.

OBJECTIVE: To compare the haemodynamic effects of identical values of continuous negative external pressure (CNEP) and positive end-expiratory pressure (PEEP) in a group of mechanically ventilated patients. SETTING: General ICU, Vicenza Hospital, Italy. PATIENTS: 15 consecutive patients, admitted after road accident trauma. METHODS: We compared the haemodynamic effects of ZEEP, 10 cmH2O of PEEP, and 10 cmH2O CNEP, applied in random order, in 15 head trauma patients under going controlled mechanical ventilation; 9 had associated thoracic trauma, while 6 did not have lung involvement. CNEP was obtained with a "poncho". RESULTS: We observed a significant increase in CI during CNEP, compared with both ZEEP and PEEP 10 cmH2O. Accordingly the oxygen delivery index significantly increased during CNEP, compared with PEEP 10 cmH2O. Conversely, Qs/Qt decreased with CNEP, if compared with PEEP, both in patients with and without lung damage. CONCLUSION: CNEP can significantly increase CI in mechanically ventilated patients in patients with and without associated lung damage.