Vibrational spectroscopy of phthalocyanine and naphthalocyanine in sandwich-type (na)phthalocyaninato and porphyrinato rare earth complexes: Part 14. The infrared and Raman characteristics of phthalocyanine in “pinwheel-like” homoleptic bis[1,8,15,22-tetrakis(3-pentyloxy)phthalocyaninato] rare earth(III) double-decker complexes

The infrared (IR) spectroscopic data and Raman spectroscopic properties for a series of 13 “pinwheel-like” homoleptic bis(phthalocyaninato) rare earth complexes M[Pc(α-OC5H11)4]2 [M = Y and Pr–Lu except Pm; H2Pc(α-OC5H11)4 = 1,8,15,22-tetrakis(3-pentyloxy)phthalocyanine] have been collected and comparatively studied. Both the IR and Raman spectra for M[Pc(α-OC5H11)4]2 are more complicated than those of homoleptic bis(phthalocyaninato) rare earth analogues, namely M(Pc)2 and M[Pc(OC8H17)8]2, but resemble (for IR) or are a bit more complicated (for Raman) than those of heteroleptic counterparts M(Pc)[Pc(α-OC5H11)4], revealing the decreased molecular symmetry of these double-decker compounds, namely S8. Except for the obvious splitting of the isoindole breathing band at 1110–1123 cm−1, the IR spectra of M[Pc(α-OC5H11)4]2 are quite similar to those of corresponding M(Pc)[Pc(α-OC5H11)4] and therefore are similarly assigned. With laser excitation at 633 nm, Raman bands derived from isoindole ring and aza stretchings in the range of 1300–1600 cm−1 are selectively intensified. The IR spectra reveal that the frequencies of pyrrole stretching and pyrrole stretching coupled with the symmetrical CH bending of –CH3 groups are sensitive to the rare earth ionic size, while the Raman technique shows that the bands due to the isoindole stretchings and the coupled pyrrole and aza stretchings are similarly affected. Nevertheless, the phthalocyanine monoanion radical Pc′− IR marker band of bis(phthalocyaninato) complexes involving the same rare earth ion is found to shift to lower energy in the order M(Pc)2 > M(Pc)[Pc(α-OC5H11)4] > M[Pc(α-OC5H11)4]2, revealing the weakened π–π interaction between the two phthalocyanine rings in the same order.

Peripherally η1-Platinated Organometallic Porphyrins as Building Blocks for Multiporphyrin Arrays

The modification of peripherally metalated meso-η1-platiniometalloporphyrins, such as trans-[PtBr(NiDAPP)(PPh3)2] (H2DAPP = 5-phenyl-10,20-bis(3‘,5‘-di-tert-butylphenyl)porphyrin), leads to the analogous platinum(II) nitrato and triflato electrophiles in almost quantitative yields. Self-assembly reactions of these meso-platinioporphyrin tectons with pyridine, 4,4‘-bipyridine, or various meso-4-pyridylporphyrins in chloroform generate new multicomponent organometallic porphyrin arrays containing up to five porphyrin units. These new types of supramolecular arrays are formed exclusively in high yields and are stable in solution or in the solid state for extended periods. They were characterized by multinuclear NMR and UV−visible spectroscopy as well as high-resolution electrospray ionization mass spectrometry.

Time-Dependent Density Functional Molecular Orbital and Excited State Calculations on Bis(porphyrinyl)butadiynes in the Monocationic, Neutral, Monoanionic, and Dianionic Oxidation States

We report a theoretical study of the multiple oxidation states (1+, 0, 1−, and 2−) of a meso,meso-linked diporphyrin, namely bis[10,15,20-triphenylporphyrinatozinc(II)-5-yl]butadiyne (4), using Time-Dependent Density Functional Theory (TDDFT). The origin of electronic transitions of singlet excited states is discussed in comparison to experimental spectra for the corresponding oxidation states of the close analogue bis{10,15,20-tris[3‘,5‘-di-tert-butylphenyl]porphyrinatozinc(II)-5-yl}butadiyne (3). The latter were measured in previous work under in situ spectroelectrochemical conditions. Excitation energies and orbital compositions of the excited states were obtained for these large delocalized aromatic radicals, which are unique examples of organic mixed-valence systems. The radical cations and anions of butadiyne-bridged diporphyrins such as 3 display characteristic electronic absorption bands in the near-IR region, which have been successfully predicted with use of these computational methods. The radicals are clearly of the “fully delocalized” or Class III type. The key spectral features of the neutral and dianionic states were also reproduced, although due to the large size of these molecules, quantitative agreement of energies with observations is not as good in the blue end of the visible region. The TDDFT calculations are largely in accord with a previous empirical model for the spectra, which was based simplistically on one-electron transitions among the eight key frontier orbitals of the C4 (1,4-butadiyne) linked diporphyrins.

Quantification of motor vehicle emission factors from on road measurements

Assessment and prediction of the impact of vehicular traffic emissions on air quality and exposure levels requires knowledge of vehicle emission factors. The aim of this study was quantification of emission factors from an on road, over twelve months measurement program conducted at two sites in Brisbane: 1) freeway type (free flowing traffic at about 100 km/h, fleet dominated by small passenger cars - Tora St); and 2) urban busy road with stop/start traffic mode, fleet comprising a significant fraction of heavy duty vehicles - Ipswich Rd. A physical model linking concentrations measured at the road for specific meteorological conditions with motor vehicle emission factors was applied for data analyses. The focus of the study was on submicrometer particles; however the measurements also included supermicrometer particles, PM2.5, carbon monoxide, sulfur dioxide, oxides of nitrogen. The results of the study are summarised in this paper. In particular, the emission factors for submicrometer particles were 6.08 x 1013 and 5.15 x 1013 particles per vehicle-1 km-1 for Tora St and Ipswich Rd respectively and for supermicrometer particles for Tora St, 1.48 x 109 particles per vehicle-1 km-1. Emission factors of diesel vehicles at both sites were about an order of magnitude higher than emissions from gasoline powered vehicles. For submicrometer particles and gasoline vehicles the emission factors were 6.08 x 1013 and 4.34 x 1013 particles per vehicle-1 km-1 for Tora St and Ipswich Rd, respectively, and for diesel vehicles were 5.35 x 1014 and 2.03 x 1014 particles per vehicle-1 km-1 for Tora St and Ipswich Rd, respectively. For supermicrometer particles at Tora St the emission factors were 2.59 x 109 and 1.53 x 1012 particles per vehicle-1 km-1, for gasoline and diesel vehicles, respectively.

The STRATIFY tool and clinical judgment were poor predictors of falling in an acute hospital setting

Objective: To compare the effectiveness of the STRATIFY falls tool with nurses’ clinical judgments in predicting patient falls. Study Design and Setting: A prospective cohort study was conducted among the inpatients of an acute tertiary hospital. Participants were patients over 65 years of age admitted to any hospital unit. Sensitivity, specificity, and positive predictive value (PPV) and negative predictive values (NPV) of the instrument and nurses’ clinical judgments in predicting falls were calculated. Results: Seven hundred and eighty-eight patients were screened and followed up during the study period. The fall prevalence was 9.2%. Of the 335 patients classified as being ‘‘at risk’’ for falling using the STRATIFY tool, 59 (17.6%) did sustain a fall (sensitivity50.82, specificity50.61, PPV50.18, NPV50.97). Nurses judged that 501 patients were at risk of falling and, of these, 60 (12.0%) fell (sensitivity50.84, specificity50.38, PPV50.12, NPV50.96). The STRATIFY tool correctly identified significantly more patients as either fallers or nonfallers than the nurses (P50.027). Conclusion: Considering the poor specificity and high rates of false-positive results for both the STRATIFY tool and nurses’ clinical judgments, we conclude that neither of these approaches are useful for screening of falls in acute hospital settings.