Wavelength-modulation-spectroscopy for real-time, in situ NO detection in combustion gases with a 5.2 μm quantum-cascade laser

A mid-infrared absorption strategy with calibration-free wavelength-modulation-spectroscopy (WMS) has been developed and demonstrated for real-time, in situ detection of nitric oxide in particulate-laden combustion-exhaust gases up to temperatures of 700 K. An external-cavity quantum-cascade laser (ECQCL) near 5.2 μm accessed the fundamental absorption band of NO, and a wavelength-scanned, 1f-normalized WMS with second-harmonic detection (WMS-2f/1f) strategy was developed. Due to the external-cavity laser architecture, large nonlinear intensity modulation (IM) was observed when the wavelength was modulated by injection-current modulation, and the IM indices were also found to be strongly wavelength-dependent as the center wavelength was scanned with piezoelectric tuning of the cavity. A quantitative model of the 1f-normalized WMS-2f signal was developed and validated under laboratory conditions. A sensor was subsequently designed, built and demonstrated for real-time, in situ measurements of NO across a 3 m path in the particulate-laden exhaust of a pulverized-coal-fired power plant boiler. The 1f-normalized WMS-2f method proved to have better noise immunity for non-absorption transmission, than wavelength-scanned direct absorption. A 0.3 ppm-m detection limit was estimated using the R15.5 transition near 1927 cm⁻¹ with 1 s averaging. Mid-infrared QCL-based NO absorption with 1f-normalized WMS-2f detection shows excellent promise for practical sensing in the combustion exhaust.     

Two-photon quantum interference from separate nitrogen vacancy centers in diamond

We report on the observation of quantum interference of the emission from two separate nitrogen vacancy (NV) centers in diamond. Taking advantage of optically induced spin polarization in combination with polarization filtering, we isolate a single transition within the zero-phonon line of the nonresonantly excited NV centers. The time-resolved two-photon interference contrast of this filtered emission reaches 66%. Furthermore, we observe quantum interference from dissimilar NV centers tuned into resonance through the dc Stark effect. These results pave the way towards measurement-based entanglement between remote NV centers and the realization of quantum networks with solid-state spins.     

Influence of solvent on the chiral resolution of organic molecules on Au(111): EC-STM study of biphenyl dicarboxylic acid on Au(111) in an aqueous environment

Adsorption-induced chiral resolution of organic molecules is important due to its potential applications in stereo-selective catalysis. We studied the adsorption-induced chiral resolution using a model achiral molecule of 4,4′ biphenyl dicarboxylic acid (BPDA) on Au(111) in 0.1 M perchloric acid (HClO₄) by electrochemical scanning tunneling microscopy (EC-STM). Our experimental data showed that the BPDA molecules formed island structures with distinctive preferred orientations at the length scale of the molecular size. The molecules did not show any orientational ordering above the length scale, indicating that chiral resolution was absent in the aqueous environment. Previously, the molecules were found to have chiral resolution on Au(111) in ultra-high vacuum conditions (UHV). We calculated angle-dependent binding energy between the substrate and a BPDA molecule, the intermolecular interactions between the BPDA molecules, and their interactions with water molecules. The calculations suggest that the absence of chiral resolution in the aqueous environment originated from the decrease in the intermolecular energy of the BPDA molecules due to their hydrogen bonds with the surrounding water molecules. The strength of the hydrogen bonding between BPDA molecules was sufficient to overcome the energy barrier for chiral resolution through rotational motion in UHV, but not in an aqueous environment.     

Photodissociation dynamics of gaseous CpCo(CO)2 and ligand exchange reactions of CpCoH2 with C3H4, C3H6, and NH3

The photodissociation dynamics of CpCo(CO)(2) was studied in a molecular beam using photofragment translational energy spectroscopy with 157 nm photoionization detection of the metallic products. At 532 and 355 nm excitation, the dominant one-photon channel involved loss of a single CO ligand producing CpCoCO. The product angular distributions were isotropic, and a large fraction of excess energy appeared as product vibrational excitation. Production of CpCO + 2CO resulted from two-photon absorption processes. The two-photon dissociation of mixtures containing CpCo(CO)(2) and H(2) at the orifice of a pulsed nozzle was used to produce a novel 16-electron unsaturated species, CpCoH(2). Transition metal ligand exchange reactions, CpCoH(2) + L → CpCoL + H(2) (L = propyne, propene, or ammonia), were studied under single-collision conditions for the first time. In all cases, ligand exchange occurred via 18-electron association complexes with lifetimes comparable to their rotational periods. Although ligand exchange reactions were not detected from CpCoH(2) collisions with methane or propane (L = CH(4) or C(3)H(8)), a molecular beam containing CpCoCH(4) was produced by photolysis of mixtures containing CpCo(CO)(2) and CH(4).     

CuII Coordination Chemistry of Patellamide Derivatives: Possible Biological Functions of Cyclic Pseudopeptides

Two synthetic derivatives of the naturally occurring cyclic pseudooctapeptides patellamide A–F and ascidiacyclamide, that is, H₄pat², H₄pat³, as well as their Cu^II complexes are described. These cyclic peptide derivatives differ from the naturally occurring macrocycles by the variation of the incorporated heterocyclic donor groups and the configuration of the amino acids connecting the heterocycles. The exchange of the oxazoline and thiazole groups by dimethylimidazoles or methyloxazoles leads to more rigid macrocycles, and the changes in the configuration of the side chains leads to significant differences in the folding of the cyclic peptides. These variations allow a detailed study of the various possible structural changes on the chemistry of the Cu^II complexes formed. The coordination of Cu^II with these macrocyclic species was monitored by high‐resolution electrospray mass spectrometry (ESI‐MS), spectrophotometric (UV/Vis) and circular dichroic (CD) titrations, and electron paramagnetic resonance (EPR) spectroscopy. Density functional theory (DFT) calculations and molecular mechanics (MM) simulations have been used to model the structures of the Cu^II complexes and provide a detailed understanding of their geometric preferences and conformational flexibility. This is related to the Cu^II coordination chemistry and the reactivity of the dinuclear Cu^II complexes towards CO₂ fixation. The variation observed between the natural and various synthetic peptide systems enables conclusions about structure–reactivity correlations, and our results also provide information on why nature might have chosen oxazolines and thiazoles as incorporated heterocycles.     

Synthesis of substituted asymmetrical biphenyl amino esters as alpha helix mimetics

As part of our ongoing project to develop new molecular probes for estrogen receptor-alpha, we are exploring the utility of internally-substituted asymmetric biphenyls as a proteomimetic scaffold. In this study, we describe synthetic methods for preparing the requisite substituted-bromophenol precursors, their further elaboration, and the subsequent Suzuki–Miyaura coupling of these sterically-hindered and electronically-rich aromatic systems. The results provide an efficient route with which to generate further libraries of novel asymmetric biphenyl compounds as potential proteomimetics.     

Molecular mass dependence of point-to-set correlation length scale in polymers

We use a recently proposed metric, termed the point-to-set correlation functions, to probe the molecular weight dependence of the relevant static length scales in glass-forming oligomeric chain liquids of 4, 5, 8, and 10 repeat units. In agreement with the results for simple, monatomic fluids, we find that static length scales of the oligomers increase monotonically when the temperature is lowered towards the glass transition temperature of the fluid. More interestingly, the static length scale increases with increasing chain length. Within the bounds of error in our simulations, the static length scale appears to scale as the radius of gyration of the oligomer, but with a prefactor, which is much larger than unity and which grows with the temperature. The preceding behavior contrasts with the length scales extracted from the radial distribution function of the oligomer system, which is practically independent of the chain length.     

Aerobic oxidation reactions catalyzed by vanadium complexes of bis(phenolate) ligands

Vanadium(V) complexes of the tridentate bis(phenolate)pyridine ligand H(2)BPP (H(2)BPP = 2,6-(HOC(6)H(2)-2,4-(t)Bu(2))(2)NC(5)H(3)) and the bis(phenolate)amine ligand H(2)BPA (H(2)BPA = N,N-bis(2-hydroxy-4,5-dimethylbenzyl)propylamine) have been synthesized and characterized. The ability of the complexes to mediate the oxidative C-C bond cleavage of pinacol was tested. Reaction of the complex (BPP)V(V)(O)(O(i)Pr) (4) with pinacol afforded the monomeric vanadium(IV) product (BPP)V(IV)(O)(HO(i)Pr) (6) and acetone. Vanadium(IV) complex 6 was oxidized rapidly by air at room temperature in the presence of NEt(3), yielding the vanadium(V) cis-dioxo complex [(BPP)V(V)(O)(2)]HNEt(3). Complex (BPA)V(V)(O)(O(i)Pr) (5) reacted with pinacol at room temperature, to afford acetone and the vanadium(IV) dimer [(BPA)V(IV)(O)(HO(i)Pr)](2). Complexes 4 and 5 were evaluated as catalysts for the aerobic oxidation of 4-methoxybenzyl alcohol and arylglycerol β-aryl ether lignin model compounds. Although both 4 and 5 catalyzed the aerobic oxidation of 4-methoxybenzyl alcohol, complex 4 was found to be a more active and robust catalyst for oxidation of the lignin model compounds. The catalytic activities and selectivities of the bis(phenolate) complexes are compared to previously reported catalysts.     

Reactions of neutral gas-phase yttrium atoms with two cyclohexadiene isomers

The reactions of neutral ground-state yttrium (Y) atoms with 1,3- and 1,4-cyclohexadiene (CHD) were studied using crossed molecular beams. Formation of YC(6)H(6) + H(2) and YH(2) + C(6)H(6) was observed for both isomers at collision energies (E(coll)) of 31.3 and 13.0 kcal/mol. Measured product branching ratios at E(coll) = 31.3 kcal/mol indicated that YH(2) + C(6)H(6) was the dominant channel, accounting for >97% of the products. An additional minor product channel, YC(4)H(4) + C(2)H(4), was observed for 1,3-CHD at the higher E(coll). The reaction threshold for YC(4)H(4) formation was determined to be 29.5 ± 2.0 kcal/mol based on fits to the data.     

Nonideal effects behind reflected shock waves in a high-pressure shock tube

Abstract. Shock tubes often experience temperature and pressure nonuniformities behind the reflected shock wave that cannot be neglected in chemical kinetics experiments. Because of increased viscous effects, smaller tube diameters, and nonideal shock formation, the reflected-shock nonidealities tend to be greater in higher-pressure shock tubes. Since the increase in test temperature () is the most significant parameter for chemical kinetics, experiments were performed to characterize in the Stanford High Pressure Shock Tube using infrared emission from a known amount of CO in argon. From the measured change in vibrationally equilibrated CO emission with time, the corresponding ddt (or for a known time interval) of the mixture was inferred assuming an isentropic relationship between post-shock temperature and pressure changes. For a range of representative conditions in argon (24–530 atm, 1275–1900 K), the test temperature 2 cm from the endwall increased 3–8 K after 100 s and 15–40 K after 500 s, depending on the initial conditions. Separate pressure measurements using a shielded piezoelectric transducer confirmed the isentropic assumption. An analytical model of the reflected-shock gas dynamics was also developed, and the calculated 's agree well with those obtained from experiment. The analytical model was used to estimate the effects of temperature and pressure nonuniformities on typical chemical kinetics measurements. When the kinetics are fast (s), the temperature increase is typically negligible, although some correction is suggested for kinetics experiments lasting longer than 500 s. The temperature increase, however, has a negligible impact on the measured laser absorption profiles of OH (306 nm) and CH (216 nm), validating the use of a constant absorption coefficient. Infrared emission experiments are more sensitive to temperature and density changes, so nonuniformities should be taken into account when interpreting ir-emission data. Received 25 April 2000 / Accepted 8 September 2000