Pulsed photothermal laser deflection for low-level smoke and NO2 measurements in engine exhausts

Pulsed Photothermal Laser Deflection (PLD) is developed to make temporally and spatially resolved measurements of NO₂ and smoke. The rapid response PLD signal is produced when a HeNe probe beam is deflected by a thermal lens produced by a pulsed XeCl-excimer laser pumped dye laser. The fast time response (30 ns) and good spatial resolution make the PLD method a candidate for future in situ measurements in turbulent engine exhausts. The PLD signals, measured in a sample cell, exhibit a linear response for NO₂ concentrations from 3 ppm to 208 ppm and for smoke concentrations from 0.3 mg/m³ to 10 mg/m³. With a low pulse energy of 4 mJ, single-shot PLD measurements in a sample cell have accuracies of ± 14 ppm for NO₂ indicating accuracies of ±0.7 mg/m³ for smoke. With increased pulse energy and multi-shot averaging, sensitivities of ± 0.4 ppm of NO₂ or ± 20 µg/m³ of smoke are expected.     

Stereodynamics of 9,11-Diphenyl-10-azatetracyclo[6.3.0.0.(4,11)0.(5,9)]undecanes. Highly Restricted Nitrogen Inversion and Isolated Phenyl Rotation. X-ray Crystallographic, Dynamic NMR, and Molecular Mechanics Studies

The (1)H NMR spectra of 10-benzyl-9,11-diphenyl-10-azatetracyclo[6.3.0.0.(4,11)0.(5,9)]undecane (BnPh(2)()) and 10-methyl-9,11-diphenyl-10-azatetracyclo[6.3.0.0.(4,11)0.(5,9)]undecane (MePh(2)()) decoalesce due to slowing inversion at nitrogen and to slowing isolated bridgehead phenyl rotation. The high nitrogen inversion barriers in MePh(2)() (DeltaG() = 12.2 +/- 0.1 kcal/mol at 250 K) and BnPh(2)() (DeltaG() = 10.6 +/- 0.1 kcal/mol at 215 K) are typical of tertiary amines in which at least one C-N-C bond angle is constrained to a small value. Compared to the minuscule rotation barriers about sp(2)-sp(3) carbon-carbon bonds in simple molecular systems, the bridgehead phenyl rotation barriers in MePh(2)() (DeltaG() = 9.8 +/- 0.1 kcal/mol at 210 K) and BnPh(2)() (DeltaG() = 9.8 +/- 0.1 kcal/mol at 210 K) are unusually high. Molecular mechanics calculations (MMX force field) suggest that the origin of the high phenyl rotation barriers lies in the close passage of an o-phenyl proton and a methyl (or benzylmethylene) proton in the transition state. BnPh(2)() crystallized from hexane as white needles in the monoclinic system Pn. Unit cell dimensions are as follows: a = 12.198(1) ?, b = 6.1399(6) ?, c = 14.938(2) ?, beta = 107.470(4) degrees, V = 1067.1(2) ?(3), Z = 2. In the crystal molecular structure, the imine bridge CNC bond angle in BnPh(2)() is constrained to a small value (96 degrees ). The benzylic phenyl group is oriented gauche to the nitrogen lone pair.