Experimental stability diagram of a diode laser subject to weakphase-conjugate feedback from a rubidium vapor cell

We report on a systematic experimental investigation of the dynamical behavior of a diode laser subject to delayed feedback from a phase-conjugating mirror based on nearly-degenerate four-wave mixing in rubidium vapor. We present the first experimental stability diagram for this system. In the weak feedback regime, with feedback levels up to -30 dB, me demonstrate locking to the pump frequency with a reduced linewidth smaller than 8 MHz. In contrast to a laser with external injection, and contrary to predictions made for phase-conjugate feedback, the extent of this locking region is found to be limited. For increased feedback rates, the laser leaves the locking region and enters an unstable region through a series of multiple sidebands spectra. This is associated with self-excitation of the relaxation oscillation, and the observed scenario suggests a series of period-doublings after an initial Hopf bifurcation     

Reactions of sperm whale myoglobin with hydrogen peroxide. Effects of distal pocket mutations on the formation and stability of the ferryl intermediate

Distal pocket mutants of sperm whale oxymyoglobin (oxy-Mb) were reacted with a 2.5-fold excess of hydrogen peroxide (HOOH) in phosphate buffer at pH 7.0, 37 degreesC. We describe a mechanism composed of three distinct steps: 1) initial oxidation of oxy- to ferryl-Mb, 2) autoreduction of the ferryl intermediate to ferric metmyoglobin (metMb), and 3) reaction of metMb with an additional HOOH molecule to regenerate the ferryl intermediate creating a pseudoperoxidase catalytic cycle. Mutation of Leu-29(B10) to Phe slows the initial oxidation reaction 3-fold but has little effect on the rate of ferryl reduction to ferric met-aquo-myoglobin. In contrast, the Val-68(E11) to Phe mutation causes a small, 60% increase in the initial oxidation reaction and a much larger 2. 5-fold increase in the rate of autoreduction. Double insertion of Phe at both the B10- and E11-positions (L29F/V68F) produces a mutant with oxidation characteristics of both single mutants, slow initial oxidation, and rapid autoreduction, but an extraordinarily high affinity for O2. Replacing His-64(E7) with Gln produces 3-4-fold increases in both processes. Combining the mutation H64Q with L29F results in a myoglobin with enhanced resistance to metMb formation in the absence of antioxidant enzymes (i.e. catalase and superoxide dismutase) due to its own high pseudoperoxidase activity, which rapidly removes any HOOH produced in the initial stages of autoxidation. This double substitution occurs naturally in the myoglobin of Asian elephants, and similar multiple replacements have been used to reduce selectively the rate of nitric oxide (NO)-induced oxidation of both recombinant MbO2 and HbO2 blood substitute prototypes without altering O2 affinity.     

Dynamic equilibrium unfolding pathway of human tumor necrosis factor-alpha induced by guanidine hydrochloride

The dynamic equilibrium unfolding pathway of human tumor necrosis factor-alpha (TNF-alpha) during denaturation at different guanidine hydrochloride (GdnHCl) concentrations (0-4.2 M) was investigated by steady-state fluorescence spectroscopy, potassium iodide (KI) fluorescence quenching, far-UV circular dichroism (CD), picosecond time-resolved fluorescence lifetime, and anisotropy decay measurements. We utilized the intrinsic fluorescence of Trp-28 and Trp-114 to characterize the conformational changes involved in the equilibrium unfolding pathway. The detailed unfolding pathway under equilibrium conditions was discussed with respect to motional dynamics and partially folded structures. At 0-0.9 M [GdnHCl], the rotational correlation times of 22-25 ns were obtained from fluorescence anisotropy decay measurements and assigned to those of trimeric states by hydrodynamic calculation. In this range, the solvent accessibility of Trp residues increased with increasing [GdnHCl], suggesting the slight expansion of the trimeric structure. At 1.2-2.1 M [GdnHCl], the enhanced solvent accessibility and the rotational degree of freedom of Trp residues were observed, implying the loosening of the internal structure. In this [GdnHCl] region, TNF-alpha was thought to be in soluble aggregates having distinct conformational characteristics from a native (N) or fully unfolded state (U). At 4.2 M [GdnHCl], TNF-alpha unfolded to a U-state. From these results, the equilibrium unfolding pathway of TNF-alpha, trimeric and all beta-sheet protein, could not be viewed from the simple two state model (N-->U).     

Phase IIa safety and immunogenicity of a therapeutic vaccine, TA-GW, in persons with genital warts

A fusion protein vaccine consisting of human papillomavirus 6 L2E7 with Alhydrogel was developed for the treatment of genital warts. Twenty-seven subjects with genital warts received 3 immunizations over 4 weeks in an open-label study. The vaccine was well-tolerated, and all subjects made serum IgG antibodies, predominantly IgG1, against L2E7. Nineteen of 25 tested persons made antigen-specific T cell proliferative responses to L2E7, and peripheral blood mononuclear cells when cultured with L2E7 in vitro produced both interferon-gamma and interleukin (IL)-5, although IL-5 predominated after the final vaccination. Five subjects completely cleared warts within 8 weeks. Subjects whose warts were not cleared by 8 weeks were offered conventional therapy. Recurrence of warts was not seen in any of the 13 persons whose warts cleared by vaccine alone or with conventional therapy. While these preliminary results of the use of this therapeutic immunogen are encouraging, proof of efficacy will require randomized double-blind trials.     

Stress formation and relaxation in amorphous Ta–Cr films

In the present paper, measurements of the intrinsic stress of thin amorphous Ta–Cr alloy films made by magnetron sputtering have been carried out. From the curvature of the substrates and by use of the Stoney formula, the stresses were determined. The bombardment of the growing film with energetic particles is shown to control the magnitude and sign of the intrinsic stress. When changing the deposition parameters, compressive or tensile stresses can be generated in the films in a range from about −2 GPa to +1 GPa. Also the stress relaxation, the change in the stress with time, has been studied for various temperatures. The stress relaxation was measured with a cantilever beam technique using a three-terminal capacitance method to detect the beam (substrate) deflection. The stress-relaxation data have been fitted to a mathematical model for stress relaxation related to inhomogeneous flow in amorphous films. This behaviour is expected to occur in the low-temperature, high-stress regime with deformation taking place along localized shear bands.     

Novel Metallic Hollow Sphere Structures

The obvious advantages of metallic hollow sphere materials have lead to several attempts to produce such structures. None of these approaches has gained practical significance owing to the very high cost of the methods. A new powder metallurgical process using styrofoam spheres allows for the production of hollow spheres from arbitrary metals and alloys. The IFAM Department of Powder Metallurgy and Composite Materials, Dresden, has developed this process and added a method that produces random hollow sphere structures (RHS) directly from the green spheres.     

Xylanases in Wheat Separation

Hemicellulases used in the wheat separation process have resulted in better separation, purer fractions, increased plant capacity, reduced processing time etc. In order to further improve enzyme-treatment in the wheat separation process, monocomponent xylanases were evaluated. A laboratory viscosity model has been set up to evaluate the xylanases. The model showed good correlation (for a commercial hemicellulase preparation used for wheat separation) between viscosity of the wheat flour slurry and the sludge/supernatant ratio after centrifugation of the slurry. A xylanase (Novozyme 867) with excellent performance in the wheat separation process has been found. The xylanase has high activity towards soluble arabinoxylan and gives a rapid viscosity reduction of wheat flour slurries. The enzyme also has a moderate activity towards insoluble arabinoxylan, but due to the low molecular weight of the solubilized material this was not was found to contribute negatively to the enzymes' performance. The pH and temperature conditions in the wheat separation process were well within the active range of the enzyme. A pilot plant experiment showed improved yield of gluten and A-starch, with no apparent negative effect on the gluten quality.     

EEM fluorescence spectroscopy as a fast method to assess the brine composition of salted herring

Ripening of barrel-salted herring (Clupea harengus) is evaluated by the use of fluorescence spectroscopy and protein determinations. During ripening, protein degradation takes place in the herring and protein is extracted into the brine. The present study aims at identifying parameters which are correlated to the ripening characteristics of barrel-salted herring and which can provide a better understanding of the ripening process. Front face fluorescence landscapes were obtained by measuring directly on the brine from barrel-salted herring. These data were analyzed by parallel factor analysis (PARAFAC), which revealed four fluorophores, tryptophan (two states), vitamin B6 and riboflavin. All four parameters showed an increase in concentration during the storage period corresponding to an increase in protein content that varied from 3 g/100 g at day 60 to 5 g/100 g after 277 days of storage. It was not possible to see a difference in the development of the four fluorophores during the ripening period. The protein content was predicted from the fluorescence landscapes by partial least squares (PLS). The use of unfolded fluorescence spectra gave an RMSECV of 0.26 g/100 g and a correlation between the measured protein content and the predicted values of 0.86.     

Influence of different carbon nanostructures on the electrocatalytic activity and stability of Pt supported electrocatalysts

Commercially available graphitized carbon nanofibers and multi-walled carbon nanotubes, two carbon materials with very different structure, have been functionalized in a nitric–sulfuric acid mixture. Further on, the materials have been platinized by a microwave assisted polyol method. The relative degree of graphitization has been estimated by means of Raman spectroscopy and X-ray diffraction while the relative concentration of oxygen containing groups has been estimated by X-ray photoelectron spectroscopy, which resulted in a graphitic character trend: Pt/GNF > Pt/F-GNF ? Pt/MWCNT > Pt/F-MWCNT. Transmission electron microscopy showed that the Pt particle size is around 3 nm for all samples, which was similar to the crystallite size obtained by X-ray diffraction. The activity towards electrochemical reduction of oxygen has been quantified using the thin-film rotating disk electrode, which has shown that all the samples have a better activity than the commercially available electrocatalysts. The trend obtained for the graphitic character maintained for the electrochemical activity, while the reverse trend has been obtained for the accelerated ageing test. Long-term potential cycling has demonstrated that the functionalization improves the stability for multi-walled carbon nanotubes, at the cost of decreased activity.