Investigation of laser induced phosphorescence and fluorescence of acetone at low pressure for molecular tagging velocimetry in gas microflows

This paper was presented at the 4th Micro and Nano Flows Conference (MNF2014), which was held at University College, London, UK. The conference was organised by Brunel University and supported by the Italian Union of Thermofluiddynamics, IPEM, the Process Intensification Network, the Institution of Mechanical Engineers, the Heat Transfer Society, HEXAG - the Heat Exchange Action Group, and the Energy Institute, ASME Press, LCN London Centre for Nanotechnology, UCL University College London, UCL Engineering, the International NanoScience Community, www.nanopaprika.eu.Laser-induced fluorescence and phosphorescence properties of gaseous acetone in argon are measured and analyzed in a pressure ranging from 10(5) to 10(2) Pa, with the aim of analyzing by molecular tagging velocimetry gas microflows in rarefied regimes which requires operation at low pressure. Acetone is excited at a wavelength of 266 nm and immediately emits short lifetime fluorescence rapidly followed by long lifetime phosphorescence. At atmospheric pressure, the early phosphorescence intensity is more than 600 times lower than the fluorescence one. The phosphorescence signal is rapidly decreasing with time, closely following a power law. Both fluorescence and phosphorescence signals are decreasing with pressure. The systematic analysis of fluorescence and phosphorescence of acetone molecules shows that although the signal is dramatically reduced at low pressure, the on-chip integration technique and the optimization of the acquisition parameters provide an exploitable signal for molecular tagging velocimetry in rarefied microflows, in a Knudsen number range corresponding to the early slip flow regime

Validation of phosphor thermometry for industrial surface temperature measurements

Surface temperature measurements are required by the aerospace and automotive industries to guarantee high-quality products and optimize production processes. Accurate and reliable measurement of surface temperature is very challenging in an industrial environment. Surface contact probes are widely used but poorly characterized, while non-contact infrared thermometry is severely hampered by the unknown emissivity of the surface and by problems caused by stray radiation from the background. An alternative approach to the above techniques is phosphor thermometry, used here in a hybrid contact/non-contact approach. In this work, the development of a lifetime-based phosphor thermometer, its application to industrial surface temperature measurement and its validation are reported in a metrologically sound manner. The phosphor thermometer was initially calibrated by contact on a reference calibrator system at the Istituto Nazionale di Ricerca Metrologica to provide SI traceability to the measurements at the industrial level; the system was later validated by exploiting a metal phase-change method. The robustness of the approach against a strong radiative background was also investigated. A comprehensive uncertainty analysis was carried out, resulting in an expanded uncertainty (k  =  2) lower than 1.4 °C over the temperature range from the ambient to 450 °C. The phosphor-based thermometer was then tested at industrial manufacturing premises to measure the surface temperature of aluminium alloy billets during the pre-heating phase before forging. The phosphor-based approach was compared with radiation and contact thermometry in both static and dynamic measurement conditions. The experimental results proved that phosphor thermometry, besides being a valid alternative to conventional techniques, may offer better performance in an industrial setting

The T1 state of p-nitroaniline and related molecules: a CNDO/S study

The nature of the lowest energy triplet state (T1) of p-nitroaniline (PNA), N,N-dimethyl-p-nitroaniline (DMPNA) and nitrobenzene (NB) is reexamd. using the semiempirical CNDO/S-CI method with selected parameter options. In the case of the unperturbed mols. the short-axis polarized p* A- singlet excitation. Computations suggest, however, that polar solvents strongly stabilize the PNA and DMPNA p* <- p charge-transfer triplet relative to other excitations, whereas specific solvent hydrogen-bonded interactions stabilize the p* <- n(s) triplet of NB below those of p* <- p character. These assignments allow a rationalization of phosphorescence lifetime data, Tn <- T1 absorption measurements and relative photochem. behavior

Iridium complex, a phosphorescent light-emitting diode material, serves as a novel chemical probe for imaging hypoxic tumor tissues

Iridium complex, a promising organic light-emitting diode for next generation television displays, emits phosphorescence. Phosphorescence is quenched by oxygen. We used this oxygen-quenching feature for imaging tumor hypoxia. Red light-emitting iridium complex Ir(btp)~2~(acac) (BTP) presented hypoxia-dependent light emission in culture cell lines, whose intensity was in parallel with HIF-1[alpha] expression. BTP was further applied to imaging five tumors (four from human origin and one from mouse origin) transplanted in athymic mice. All tumors presented a bright BTP-emitting image even 5 min after the injection. The BTP-dependent tumor image peaked at 1 to 2 h after the injection, and was then cleared from tumors within 24 h. The minimal BTP image recognition size was 3 to 4 mm in diameter. Compared with ^18^F-FDG/PET images, BTP delineated a clearer image for a tumor profile. We suggest that iridium complex has a vast potential for imaging hypoxic lesions such as tumor tissues

Excimer formation by steric twisting in carbazole and triphenylamine-based host materials

This paper presents a detailed spectroscopic investigation of luminescence properties of 4,4′-Bis(N-carbazolyl)-1,1′-biphenyl (CBP) and N,N,N’,N’-tetraphenylbenzidine (TAD) in solutions and neat films. These compounds are compared to their derivatives CDBP and TDAD that contain methyl groups in the 2 and 2’ position of the biphenyl core. We find that whereas steric twisting in CDBP and TDAD leads to a high triplet energy of about 3.0 and 3.1 eV, respectively, these compounds also tend to form triplet excimers in a neat film, in contrast to CBP and TAD. By comparison with N-phenylcarbazole (NPC) and triphenylamine (TPA), on which these compounds are based, as well as with the rigid spiro analogs to CBP and TAD we show that the reduced excimer formation in CBP and TAD can be attributed to a localization of the excitation onto the central biphenyl part of the molecule

Amplified singlet oxygen generation in metallated-porphyrin doped conjugated polymer nanoparticles

We report on the mechanism and efficiencies of singlet oxygen O2(1Δg) generation of nanoparticles (NP) of the conjugated polymer (CP) poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT) doped with platinum octaethylporphyrin (PtOEP) suspended in water. A detailed study of the photophysics of these NP, using stationary and time-resolved absorption and emission techniques, indicates that O2(1Δg) is generated by the triplet excited state of F8BT and not by that of PtOEP, as previously observed for other porphyrin doped CP NP. O2(1Δg) quantum yields (ΦΔ) were measured by quantifying the characteristic phosphorescence of O2(1Δg) in the NIR region (∼1268 nm). It was found that incorporation of relatively small amounts of PtOEP to F8BT NP results in a significant increase of ΦΔ. NP containing 10% PtOEP (w/w) show a ΦΔ ∼ 0.24, which is 3 times larger than that observed for undoped F8BT NP, and larger than the reported for most water-soluble porphyrins. ΦΔ were also calculated from the oxidation rates (v0) of 3-[10-(2-carboxyethyl)anthracen-9-yl]propanoic acid (ADPA), a well-known chemical O2(1Δg) trap. Unexpectedly, this method was found to significantly overestimate the ΦΔ values due to the adsorption of ADPA on the surface of NP. The ADPA/NP adsorption process was characterized using a simple adsorption model yielding an (average) equilibrium constant of ∼8 × 103 M−1 and an (average) number of NP-binding sites of ∼14000. These results necessarily caution about the use of ADPA as a probe to evaluate ΦΔ in these NP systems. In addition, the interaction of F8BT NP with other anionic, cationic and zwitterionic dyes (dissolved in water) was studied. It was found that even at nano-molar concentrations all the dyes efficiently adsorb on the NP surface. This general and simple self-assembly strategy can be used to prepare superficially-dye-doped CP NP with potentially interesting technological applications.Fil: Spada, Ramiro Martín. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; ArgentinaFil: Macor, Lorena Paola. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Hernández, Laura. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Ponzio, Rodrigo Andrés. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; ArgentinaFil: Ibarra, Luis Exequiel. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Biología Molecular; ArgentinaFil: Lorente, Carolina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Chesta, Carlos Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; ArgentinaFil: Palacios, Rodrigo Emiliano. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentin

Coherent energy migration in solids: Determination of the average coherence length in one‐dimensional systems using tunable dye lasers

The coherent nature of energy propagation in solids at low temperatures was established from the time resolved response of the crystal to short optical pulses obtained from a dye laser (pumped by a nitrogen gas laser). The trapping and detrapping of the energy by shallow defects (x traps) was evident in the spectra and enabled us to extract the coherence length: l≳700 Å=186 molecules for the one‐dimensional triplet excitons of 1,2,4,5‐tetrachlorobenzene crystals at T<4.2° K. This length which clearly exceeds the stochastic random walk limit is related to the thermalization mechanisms in this coupled exciton–trap system, and its magnitude supports the notion that exciton–phonon coupling is responsible for the loss of coherence on very long molecular chains (trap concentration is 1/256 000)

Fluorescence and phosphorescence from individual C60_{60} molecules excited by local electron tunneling

Using the highly localized current of electrons tunneling through a double barrier Scanning Tunneling Microscope (STM) junction, we excite luminescence from a selected C$_{60}$ molecule in the surface layer of fullerene nanocrystals grown on an ultrathin NaCl film on Au(111). In the observed luminescence fluorescence and phosphorescence spectra, pure electronic as well as vibronically induced transitions of an individual C$_{60}$ molecule are identified, leading to unambiguous chemical recognition on the single-molecular scale