Rotationally resolved absorption cross sections of formaldehyde in the 28100-28500 cm(-1) (351-356 nm) spectral region: implications for in situ LIF measurements

The rotationally resolved ultraviolet absorption cross sections for the 2(0)(0)4(1)(0) vibrational band of the A(1)A(2)-X(1)A(1) electronic transition of formaldehyde (HCHO) at an apodized resolution of 0.027 cm(-1) (approximately 0.0003 nm at 352 nm) over the spectral range 28100-28500 cm(-1) (351-356 nm) at 298 and 220 K, using Fourier transform spectroscopy, are first reported here. Accurate rotationally resolved cross sections are important for the development of in situ HCHO laser-induced fluorescence (LIF) instruments and for atmospheric monitoring. Pressure dependence of the cross sections between 75 and 400 Torr at 298 K was explored, and an average pressure broadening coefficient in dry air of 1.8 x 10(-4) cm(-1) Torr(-1) for several isolated lines is reported. Gaseous HCHO was quantitatively introduced into a flow cell by evaporating micron-sized droplets of HCHO solution, using a novel microinjector technique. The condensed-phase concentrations of HCHO were determined by iodometric titrations to an accuracy of <1%. Accuracy of the measured absorption cross sections is estimated to be better than +/-5%. Integrated and differential cross sections over the entire band at low resolution (approximately 1 cm(-1)) obtained with our calibration technique are in excellent agreement with previous measurements. A maximum differential cross section of 5.7 x 10(-19) cm(2) molecule(-1) was observed at high resolution-almost an order of magnitude greater than any previously reported data at low resolution.     

Numerical investigation of coexisting high and low amplitude responses and safe basin erosion for a coupled linear oscillator and nonlinear absorber system

Over the last half century, numerous nonlinear variants of the tuned mass damper have been developed in order to improve attenuation characteristics. In the present study, the performance of a linear oscillator and an absorber with a strongly nonlinear cubic stiffness is evaluated by using numerical methods. This configuration has been of recent interest due to its capability of wide-band energy absorption. However, high amplitude solutions, which would amplify the response of the system, have been shown to often coexist with the low amplitude solutions. The present research is focused on numerically determining the relative strength of the coexisting solutions. Erosion profiles are presented, quantifying the integrity of the system, i.e. the likelihood of converging to a safe, low amplitude response, and providing an indication of the structural safety of a practical absorber system. The results indicate that the high amplitude solutions not only exist but significantly influence the response of the system within the range of expected operating conditions, particularly at excitation frequencies lower than the natural frequency of the linear oscillator. The erosion profiles indicate a 20–40% increase in system integrity for the case of zero damping compared to a small amount of damping, no significant integrity change when adding a small linear stiffness component to the nonlinear absorber, and no significant change in integrity between the midpoint and extreme of the bi-stable range. Additional higher-period solutions are also discovered and evidence of a chaotic response is presented.     

A Bayesian approach to seafloor classification using multi-beam echo-sounder backscatter data

Seafloor classification using acoustic remote sensing techniques is an attractive approach due to its high-coverage capabilities and limited costs. The multi-beam echo-sounder (MBES) system provides high-resolution bathymetry and backscatter information with 100% coverage. In this paper, we present a seafloor classification method that employs the MBES backscatter data. The method uses the averaged backscatter data per beam. It, therefore, is independent on the quality of the MBES calibration. Also, its performance is insensitive to seafloor type variation along the MBES swathe and corrections for the angular dependence of the backscatter are not needed. The method accounts for the ping-to-ping variability of the backscatter intensity. It estimates both the number of seafloor types present in the survey area and the probability density function for the backscatter strength at a certain angle for each of the seafloor types. Application of the method to MBES backscatter data acquired in a well-known test area in the North Sea shows very good agreement with available ground truth. The method’s discriminatory performance for this area is demonstrated to be comparable to that of taking samples of the sediment. All seafloor types known to be present in the area are resolved for. Application of the method to the Stanton bank data set shows clearly separable areas that differ in seafloor composition.     

Maximum coefficient of light extinction in a nonabsorbing dispersive medium

The maximum value of the light extinction coefficient μ, which can be observed in a dispersive medium with a relative refractive index n of the scattering particles, is studied within the framework of a quasi-crystalline approximation for nonabsorbing dispersive media consisting of monodisperse spherical scatterers. A change in the diffraction parameter x of the scattering particles and their volume concentration c _v is accompanied by nonmonotonic variations of the extinction coefficient, and the function μ(x, c _v ) exhibits several maxima. The dimensions and concentrations of particles are determined, for which the extinction coefficient reaches the absolute maximum μ^max. The μ^max value exhibits a monotonic growth with increasing relative refractive index n of the scattering particles. The conditions of validity of the Ioffe-Regel criterion of radiation localization have been studied. It is established that the localization in nonabsorbing dispersive media can be observed only for n ? 2.7. The intervals of x and c _v in which the criterion of radiation localization is satisfied in dispersive media consisting of particles with n = 3.0 and 3.5 are determined.     

Haloalkane dehalogenase catalysed desymmetrisation and tandem kinetic resolution for the preparation of chiral haloalcohols

Six different bacterial haloalkane dehalogenases were recombinantly produced in Escherichia coli, purified, and used to catalyse the conversion of prochiral short-chain dihaloalkanes and a meso dihaloalkane, yielding enantioenriched haloalcohols. A two-reaction one-enzyme process was established in which the desymmetrisation of a dihaloalkane is followed by kinetic resolution of the chiral haloalcohol that is produced in the first step. In case of 1,3-dibromo-2-methylpropane and 1,3-dibromo-2-phenylpropane, an increase of the enantiomeric excess of the respective haloalcohol was observed in time, leading to ee values of >97%, with analytical yields of 24 and 52%, respectively. The results show that haloalkane dehalogenases can be used for the production of highly enantioenriched haloalcohols and that in some cases product enantiopurity can be improved by allowing a two-step one-enzyme tandem reaction.     

Citrate selectivity of poly(neutral red) electropolymerized films

The synthesis and the spectroscopic and potentiometric characterization of electropolymerized films obtained from neutral red (NR) on Pt surface are described. FT Raman and NMR spectroscopy were used for evaluation of the resulting poly(NR) layers. Then potentiometry was applied to study the characteristics of the complexation of carboxylates with the poly(NR) films. A potentiometric poly(NR) sensor showing high selectivity for citrate anion was employed for its determination in soft drinks.     

Low-frequency cooperative dynamics in L-, D-, and DL-alanine crystals: a 13C and 15N cross-polarization magic-angle-spinning NMR study

Knowledge of the dynamical changes in molecular configurations in various amino acid structures over a wide range of time scales is important since such changes may influence the structural transformations and the diverse biological functionalities of proteins. Using the temperature dependence of the rotating-frame NMR spin-lattice relaxation times T(1rho) of protons as a probe, we have investigated the low-frequency (approximately 60-100 kHz) dynamics in the crystal structures of L-, D-, and DL- alanine (C(12)H(28)O(8)N(4)) polymorphs. The proton relaxation times T(1rho) were obtained from (13)C <-- (1)H and (15)N <-- (1)H cross-polarization magic-angle-spinning NMR experiments over a temperature range of 192-342 K. The data reveal that the time scales of these low-frequency dynamical processes are distinctly different from the localized, high-frequency rotational motion of methyl and amine groups. The strongly asymmetric T(1rho) versus temperature curves and the subtle dynamical differences between the DL-alanine and the L- and d-enantiomorphs indicate that these low-frequency processes are cooperative in nature and are sensitive to molecular packing.     

Dynamic kinetic resolution of racemic beta-haloalcohols: direct access to enantioenriched epoxides

The direct chemo-enzymatic DKR of racemic beta-haloalcohols is reported, yielding the corresponding optically active epoxides in a single step. The mutant haloalcohol dehalogenase HheC Cys153Ser Trp249Phe is used for the asymmetric ring closure, whereas racemization of the remaining enantiomer of the haloalcohol is achieved using the new iridacycle 3, one of the most effective racemization catalysts to date for beta-haloalcohols.     

Stress distribution in a lap joint under tension-shear

This paper deals with the elastostatic load transfer of a tensile load in a model of an adhesive lap joint (tension-shear problem). The adhesive layer is regarded as infinitesimally thin and the displacement and traction vectors in the adherends are assumed to be continuous across the bond. The problem is reduced to a pair of Fredholm integral equations of the second kind which involve the mean angle between the deformed bond line and the tensile load. This angle, in turn, is determined by means of a scheme due to Goland and Reissner. Numerical results for the bond line stresses and the stress intensity factors at the ends of the bonded region are presented.