Wavelength-agile H2O absorption spectrometer for thermometry of general combustion gases

Using a novel Fourier-domain mode-locking (FDML) laser scanning 1330-1380 nm, we have developed a gas thermometer based on absorption spectroscopy that is appropriate for combustion gases at essentially arbitrary conditions. The path-integrated measurements are particularly useful in homogeneous environments, and here we present measurements in a controlled piston engine and a shock tube. Engine measurements demonstrate a RMS temperature precision of ±3% at 1500 K and 200 kHz bandwidth; the precision is improved dramatically by averaging. Initial shock tube measurements place the absolute accuracy of the thermometer within ∼2% to 1000 K. The sensor performs best when significant H₂O vapor is present, but requires only at 300 K, at 1000 K, or at 3000 K for 2% accurate thermometry, assuming a 4 kHz measurement bandwidth (200 kHz scans with 50 averages). The sensor also provides H₂O mole fraction and shows potential for monitoring gas pressure based on the broadening of spectral features. To aid in designing other sensors based on high-temperature, high-pressure H₂O absorption spectroscopy, a database of measured spectra is included.     

Experimental evidence for a light and broad scalar resonance in D(+) --> pi(-)pi(+)pi(+) decay

From a sample of 1172 +/- 61 D(+)-->pi(-)pi(+)pi(+) decays, we find gamma(D(+)-->pi(-)pi(+)pi(+))/gamma(D(+)-->K-pi(+)pi(+)) = 0.0311 +/- 0.0018(+0.0016)(-0.0026). Using a coherent amplitude analysis to fit the Dalitz plot of these decays, we find strong evidence that a scalar resonance of mass 478(+24)(-23) +/- 17 MeV/c(2) and width 324(+42)(-40) +/- 21 MeV/c(2) accounts for approximately half of all decays.     

Solid-phase Pd-catalysed cross-coupling methods for the construction of π-conjugated peptide nanomaterials

We describe the development of two procedures for the synthesis of peptides that are embedded with a variety of π-conjugated semi-conducting oligomers. These procedures utilise solid-phase variants of classical palladium-catalysed cross-couplings commonly used to prepare π-conjugated oligomers. The resulting peptide–π–electron hybrids are soluble in aqueous media and self-assemble to produce 1D nanostructures, simultaneously forming networks of π-stacked conduits. The procedures have allowed for the inclusion of complex chromophores including mixed aryl units, ethynylene linkers and sexithiophenes where the latter peptide's nanostructures demonstrated substantial conductivity when employed as an active layer in a field-effect transistor.     

Optimization of Biocompatibility for a Hydrophilic Biological Molecule Encapsulation System

Despite considerable advances in recent years, challenges in delivery and storage of biological drugs persist and may delay or prohibit their clinical application. Though nanoparticle-based approaches for small molecule drug encapsulation are mature, encapsulation of proteins remains problematic due to destabilization of the protein. Reverse micelles composed of decylmonoacyl glycerol (10MAG) and lauryldimethylamino-N-oxide (LDAO) in low-viscosity alkanes have been shown to preserve the structure and stability of a wide range of biological macromolecules. Here, we present a first step on developing this system as a future platform for storage and delivery of biological drugs by replacing the non-biocompatible alkane solvent with solvents currently used in small molecule delivery systems. Using a novel screening approach, we performed a comprehensive evaluation of the 10MAG/LDAO system using two preparation methods across seven biocompatible solvents with analysis of toxicity and encapsulation efficiency for each solvent. By using an inexpensive hydrophilic small molecule to test a wide range of conditions, we identify optimal solvent properties for further development. We validate the predictions from this screen with preliminary protein encapsulation tests. The insight provided lays the foundation for further development of this system toward long-term room-temperature storage of biologics or toward water-in-oil-in-water biologic delivery systems.     

Anthropogenic changes of nitrogen loads in a small river: external nutrient sources vs. internal turnover processes

Anthropogenic nutrient inputs increase the N-load in many aquatic systems, leading to eutrophication and potential changes of biological N-retention capacity. In this study, nitrate inputs in a small river were investigated along a gradient of anthropogenic influence. We aimed to determine changes in nitrate load and isotope signatures in the water column and to identify the anthropogenic influence on biological nitrogen assimilation and nitrification or denitrification in sediments. In seasonal sampling campaigns, we analysed dissolved inorganic nitrogen concentrations, and stable isotopes of nitrate. To differentiate rates of nitrate production and consumption in the pristine vs. agricultural river section, intact sediment cores were incubated with ¹⁵N-labelled nitrate. δ¹⁵N values of nitrate in the pristine river section were low, reflecting natural sources, but, as expected, increased with nitrate concentration in all seasons along the gradient. In general, nitrate retention and consumption were higher in the anthropogenically impacted than in the pristine river section, and nitrate consumption exceeded production. In addition to our measurements, modelled results also show that even in a small river, the anthropogenically enhanced consumption capacity is overwhelmed by surplus N-inputs, and nitrate consumption cannot increase in turn with external loads.     

Objectively discerning Autler-Townes splitting from electromagnetically induced transparency

Autler-Townes splitting (ATS) and electromagnetically induced transparency (EIT) both yield transparency in an absorption profile, but only EIT yields strong transparency for a weak pump field due to Fano interference. Empirically discriminating EIT from ATS is important but so far has been subjective. We introduce an objective method, based on Akaike's information criterion, to test ATS vs EIT from experimental data for three-level atomic systems and determine which pertains. We apply our method to a recently reported induced-transparency experiment in superconducting-circuit quantum electrodynamics.     

Equivalence of the (Generalised) Hadamard and Microlocal Spectrum Condition for (Generalised) Free Fields in Curved Spacetime

We prove that the singularity structure of all n-point distributions of a state of a generalised real free scalar field in curved spacetime can be estimated if the two-point distribution is of Hadamard form. In particular this applies to the free field and the result has applications in perturbative quantum field theory, showing that the class of all Hadamard states is the state space of interest. In our proof we assume that the field is a generalised free field, i.e. that it satisfies scalar (c-number) commutation relations, but it need not satisfy an equation of motion. The same arguments also work for anti-commutation relations and for vector-valued fields. To indicate the strengths and limitations of our assumption we also prove the analogues of a theorem by Borchers and Zimmermann on the self-adjointness of field operators and of a weak form of the Jost-Schroer theorem. The original proofs of these results make use of analytic continuation arguments. In our case no analyticity is assumed, but to some extent the scalar commutation relations can take its place.     

Infrared and Raman spectra, conformational stability, ab initio calculations, and vibrational assignments for methylaminothiophosphoryl difluoride

Infrared spectra (4000–50 cm⁻¹) of the vapor, amorphous and crystalline solids and Raman spectra (3600–10 cm⁻¹) of the liquid with qualitative depolarization data as well as the amorphous and crystalline solids of methylaminothiophosphoryl difluoride, CH₃N(H)P(=S)F₂, and three deuterated species, CD₃N(H)P(=S)F₂, CH₃N(D)P(=S)F₂, and CD₃N(D)P(=S)F₂, have been recorded. The spectra indicate that in the vapor, liquid and amorphous solid a small amount of a second conformer is present, whereas only one conformer remains in the low temperature crystalline phase. The near-infrared spectra of the vapor confirms the existence of two conformers in the gas phase. Asymmetric top contour simulation of the vapor shows that the trans conformer is the predominant vapor phase conformer. From a temperature study of the Raman spectrum of the liquid the enthalpy difference between the trans and near-cis conformers was determined to be 368±15 cm⁻¹ (4.41±0.2 kJ/mol), with the trans conformer being thermodynamically preferred. Ab Initio calculations with structure optimization using the 6-31G(d) and 6-311+G(d,p) basis sets at the restricted Hartree–Fock (RHF) and/or with full electron correlation by the perturbation method to second order (MP2) support the occurrence of near-trans (5° from trans) and near-cis (20° from cis) conformers. From the RHF/6-31G(d) calculation the near-trans conformer is predicted to be the more stable form by 451 cm⁻¹ (5.35 kJ/mol) and from the MP2/6-311+G(d,p) calculation by 387 cm⁻¹ (4.63 kJ/mol). All of the normal modes of the near-trans rotamer have been assigned based on infrared band contours, depolarization values and group frequencies and the assignment is supported by the normal coordinate calculation utilizing harmonic force constants from the MP2/6-31G(d) ab initio calculations.