Dynamic light scattering and optical absorption spectroscopy study of pH and temperature stabilities of the extracellular hemoglobin of Glossoscolex paulistus

The extracellular hemoglobin of Glossoscolex paulistus (HbGp) is constituted of subunits containing heme groups, monomers and trimers, and nonheme structures, called linkers, and the whole protein has a minimum molecular mass near 3.1 x 10(6) Da. This and other proteins of the same family are useful model systems for developing blood substitutes due to their extracellular nature, large size, and resistance to oxidation. HbGp samples were studied by dynamic light scattering (DLS). In the pH range 6.0-8.0, HbGp is stable and has a monodisperse size distribution with a z-average hydrodynamic diameter (D-h) of 27 +/- 1 nm. A more alkaline pH induced an irreversible dissociation process, resulting in a smaller D-h of 10 +/- 1 nm. The decrease in D-h suggests a complete hemoglobin dissociation. Gel filtration chromatography was used to show unequivocally the oligomeric dissociation observed at alkaline pH. At pH 9.0, the dissociation kinetics is slow, taking a minimum of 24 h to be completed. Dissociation rate constants progressively increase at higher pH, becoming, at pH 10.5, not detectable by DILS. Protein temperature stability was also pH-dependent. Melting curves for HbGp showed oligomeric dissociation and protein denaturation as a function of pH. Dissociation temperatures were lower at higher pH. Kinetic studies were also performed using ultraviolet-visible absorption at the Soret band. Optical absorption monitors the hemoglobin autoxidation while DLS gives information regarding particle size changes in the process of protein dissociation. Absorption was analyzed at different pH values in the range 9.0-9.8 and at two temperatures, 25 degrees C and 38 degrees C. At 25 degrees C, for pH 9.0 and 9.3, the kinetics monitored by ultraviolet-visible absorption presents a monoexponential behavior, whereas for pH 9.6 and 9.8, a biexponential behavior was observed, consistent with heme heterogeneity at more alkaline pH. The kinetics at 38 degrees C is faster than that at 25 degrees C and is biexponential in the whole pH range. DLS dissociation rates are faster than the autoxidation dissociation rates at 25 degrees C. Autoxiclation and dissociation processes are intimately related, so that oligomeric protein dissociation promotes the increase of autoxidation rate and vice versa. The effect of dissociation is to change the kinetic character of the autoxidation of hemes from monoexponential to biexponential, whereas the reverse change is not as effective. This work shows that DLS can be used to follow, quantitatively and in real time, the kinetics of changes in the oligomerization of biologic complex supramolecular systems. Such information is relevant for the development of mimetic systems to be used as blood substitutes.

Direct Solid-Phase Optical Measurements in Flow Systems: A Review

Measurements based on absorption, reflectance, or luminescence of molecular species or complex ions can be carried out directly on a solid support simultaneously to the retention of the analyte. The use of this strategy in flow-based systems is advantageous in view of the reproducible handling of solutions in retention and elution steps of the analyte. This approach can be exploited to increase sensitivity, minimize reagent consumption as well as waste generation, improve selectivity or for simultaneous determination based on selective retention or differences in sorption rates of the analytes. This review focuses on the main characteristics of direct solid-phase measurements in flow systems, including the discussion of advantages and limitations and practical guidelines to the successful implementation of this approach. Selected applications in diverse fields, such as pharmaceutical, food, and environmental analysis are discussed.

Evaluation of the use of multiple lines for determination of metals in water by inductively coupled plasma optical emission spectrometry with axial viewing

Inductively coupled plasma optical emission spectrometers (ICP DES) allow fast simultaneous measurements of several spectral lines for multiple elements. The combination of signal intensities of two or more emission lines for each element may bring such advantages as improvement of the precision, the minimization of systematic errors caused by spectral interferences and matrix effects. In this work, signal intensities for several spectral lines were combined for the determination of Al, Cd, Co, Cr, Mn, Pb, and Zn in water. Afterwards, parameters for evaluation of the calibration model were calculated to select the combination of emission lines leading to the best accuracy (lowest values of PRESS-Predicted error sum of squares and RMSEP-Root means square error of prediction). Limits of detection (LOD) obtained using multiple lines were 7.1, 0.5, 4.4, 0.042, 3.3, 28 and 6.7 mu g L(-1) (n = 10) for Al, Cd. Co, Cr, Mn, Pb and Zn, respectively, in the presence of concomitants. On the other hand, the LOD established for the most intense emission line were 16. 0.7, 8.4, 0.074. 23, 26 and 9.6 mu g L(-1) (n = 10) for these same elements in the presence of concomitants. The accuracy of the developed procedure was demonstrated using water certified reference material. The use of multiple lines improved the sensitivity making feasible the determination of these analytes according to the target values required for the current environmental legislation for water samples and it was also demonstrated that measurements in multiple lines can also be employed as a tool to verify the accuracy of an analytical procedure in ICP DES. (C) 2009 Elsevier B.V. All rights reserved.

Partial microwave-assisted wet digestion of animal tissue using a baby-bottle sterilizer for analyte determination by inductively coupled plasma optical emission spectrometry

A procedure for partial digestion of bovine tissue is proposed using polytetrafluoroethylene (PTFE) microvessels inside a baby-bottle sterilizer under microwave radiation for multi-element determination by inductively coupled plasma optical emission spectrometry (ICP OES). Samples were directly weighed in laboratory-made polytetrafluoroethylene vessels. Nitric acid and hydrogen peroxide were added to the uncovered vessels, which were positioned inside the baby-bottle sterilizer, containing 500 mL of water. The hydrogen peroxide volume was fixed at 100 mu L The system was placed in a domestic microwave oven and partial digestion was carried out for the determination of Ca, Cu, Fe. Mg, Mn and Zn by inductively coupled plasma optical emission spectrometry. The single-vessel approach was used in the entire procedure, to minimize contamination in trace analysis. Better recoveries and lower residual carbon content (RCC) levels were obtained under the conditions established through a 2(4-1) fractional factorial design: 650 W microwave power, 7 min digestion time, 50 mu L nitric acid and 50 mg sample mass. The digestion efficiency was ascertained according to the residual carbon content determined by inductively coupled plasma optical emission spectrometry. The accuracy of the proposed procedure was checked against two certified reference materials. (C) 2009 Elsevier B.V. All rights reserved.

Thermal, structural and optical properties of Al(2)CoO(4)-Crocoite composite nanoparticles used as pigments

Al(2)CoO(4)-PbCrO(4) and Al(2)CoO(4)-Pb(2)CrO(5) crystalline powders in different proportions were obtained by the polymeric precursor method. Differential scanning calorimetry (DSC) and thermogravimetry (TG) techniques were used to accurately characterize the distinct thermal events occurring during synthesis. The TG and DSC results revealed a series of overlapping decomposition reactions due to different exothermal events, which were identified as H(2)O and NO(x) elimination and polymer pyrolysis. The X-ray diffraction patterns of the xAl(2)CoO(4)-(1 - x)PbCrO(4) and xAl(2)CoO(4)-(1 - x)Pb(2)CrO(5) mixed compounds, with x = 1, 0.75, 0.5, 0.25 and 0, were obtained in the crystalline form with their respective phases, and proved consistent with the nominal compositions. The synthesis of these two systems yielded nine different colors and shades.

Sensorless synchronization method for thin-film direct optical broadband monitoring system

Optical monitoring systems are necessary to manufacture multilayer thin-film optical filters with low tolerance on spectrum specification. Furthermore, to have better accuracy on the measurement of film thickness, direct monitoring is a must. Direct monitoring implies acquiring spectrum data from the optical component undergoing the film deposition itself, in real time. In making film depositions on surfaces of optical components, the high vacuum evaporator chamber is the most popular equipment. Inside the evaporator, at the top of the chamber, there is a metallic support with several holes where the optical components are assembled. This metallic support has rotary motion to promote film homogenization. To acquire a measurement of the spectrum of the film in deposition, it is necessary to pass a light beam through a glass witness undergoing the film deposition process, and collect a sample of the light beam using a spectrometer. As both the light beam and the light collector are stationary, a synchronization system is required to identify the moment at which the optical component passes through the light beam.

Theoretical and Experimental Study of Polarization Dependent Loss in a Optical Recirculating Loop

An experimental study of the Polarization Dependent Loss (PDL) is performed in an Optical Recirculating Loop (RCL). The RCL enables to simulate the transmission through various optical links using just one optical fiber spool, one in line amplifier, some optical filters and devices in a low cost manner. The total amount of PDL in a Recirculating loop, due to its statistical nature, is different of the simple sum of each element of the recirculating loop because of the alignment variation of the PDL elements with time, depending on the environmental conditions such as fiber stress and temperature. In this paper theoretical studies are also performed using formalism of Jones and Mueller matrices in order to represent the different optical elements in the recirculating loop. The PDL must be correctly characterized in order to evaluate properly the impact on the performance of next generation DWDM systems. Theoretical and experimental results comparison shows that a depolarization of 7% occurs in the experimental setup, probably by the optical amplifier due to the depolarized nature of the amplified spontaneous emission.

A Cost-Benefit Analysis on Modulation Formats for 40-Gb/s Optical Communication Systems

This article discusses possible approaches for optical network capacity upgrade by considering the use of different modulation formats at 40 Gb/s. First, a performance evaluation is carried out regarding tolerance to three impairments: spectral narrowing due to filter cascading, chromatic dispersion, and self-phase modulation. Next, a cost-benefit analysis is conducted, considering the specific optoelectronic components required for the optical transmitter/receiver configuration of each format.

Connection Admission Control for a WDM Optical Network Based on Traffic Monitoring and Bandwidth Release

We proposed a connection admission control (CAC) to monitor the traffic in a multi-rate WDM optical network. The CAC searches for the shortest path connecting source and destination nodes, assigns wavelengths with enough bandwidth to serve the requests, supervises the traffic in the most required nodes, and if needed activates a reserved wavelength to release bandwidth according to traffic demand. We used a scale-free network topology, which includes highly connected nodes ( hubs), to enhance the monitoring procedure. Numerical results obtained from computational simulations show improved network performance evaluated in terms of blocking probability.

Phase-only optical encryption based on the zeroth-order phase-contrast technique

A phase-only encryption/decryption scheme with the readout based on the zeroth-order phase-contrast technique (ZOPCT), without the use of a phase-changing plate on the Fourier plane of an optical system based on the 4f optical correlator, is proposed. The encryption of a gray-level image is achieved by multiplying the phase distribution obtained directly from the gray-level image by a random phase distribution. The robustness of the encoding is assured by the nonlinearity intrinsic to the proposed phase-contrast method and the random phase distribution used in the encryption process. The experimental system has been implemented with liquid-crystal spatial modulators to generate phase-encrypted masks and a decrypting key. The advantage of this method is the easy scheme to recover the gray-level information from the decrypted phase-only mask applying the ZOPCT. An analysis of this decryption method was performed against brute force attacks. (C) 2009 Society of Photo-Optical Instrumentation Engineers. [DOI: 10.1117/1.3223629]

Birefringence enhancement by using D-shaped microstructured optical fibers

In this study, a detailed numerical investigation is presented, seeking to enhance the birefringence effect by using D-shaped microstructured optical fibers (MOFs). We studied a D-shape core geometry associated with three different air-hole configurations: circular and elliptical, aligned with either the x-direction or the y-direction. Results have shown that ultrahigh birefringence MOFs, with B values of the order of 10(-2) for a wide range of wavelengths, can be obtained. The highest birefringence B was equal 3.97 x 10(-2), a value found for a D-MOF (circular holes) at 1550 nm. To the best of our knowledge, this is the highest theoretical value in the published literature.

Performance analysis of an optical network employing waveband and traffic grooming

This paper analyses an optical network architecture composed by an arrangement of nodes equipped with multi-granular optical cross-connects (MG-OXCs) in addition to the usual optical cross-connects (OXCs). Then, selected network nodes can perform both waveband as well as traffic grooming operations and our goal is to assess the improvement on network performance brought by these additional capabilities. Specifically, the influence of the MG-OXC multi-granularity on the blocking probability is evaluated for 16 classes of service over a network based on the NSFNet topology. A mechanism of fairness in bandwidth capacity is also added to the connection admission control to manage the blocking probabilities of all kind of bandwidth requirements. Comprehensive computational simulation are carried out to compare eight distinct node architectures, showing that an adequate combination of waveband and single-wavelength ports of the MG-OXCs and OXCs allow a more efficient operation of a WDM optical network carrying multi-rate traffic.

A novel subwavelength plasmon-polariton optical filter based on tilted coupled structures

This work proposes a completely new approach for the design of resonant structures aiming at wavelength-filtering applications. The structure consists of a subwavelength metal-insulator-metal (MIM) waveguide presenting tilted coupled structures transversely arranged in the midpoint between the input and output ports. The cavity-like response of this device has shown that this concept can be particularly attractive for optical filter design for telecom applications. The extra degree of freedom provided by the tilting of the cavity has proved to be not only very effective on improving the quality factor of these structures, but also to be an elegant way of extending the range of applications for tuning multiple wavelengths, if necessary.

Finite element homogenization technique for the characterization of d(15) shear piezoelectric macro-fibre composites

A finite element homogenization method for a shear actuated d(15) macro-fibre composite (MFC) made of seven layers (Kapton, acrylic, electrode, piezoceramic fibre and epoxy composite, electrode, acrylic, Kapton) is proposed and used for the characterization of its effective material properties. The methodology is first validated for the MFC active layer only, made of piezoceramic fibre and epoxy, through comparison with previously published analytical results. Then, the methodology is applied to the seven-layer MFC. It is shown that the packaging reduces significantly the shear stiffness of the piezoceramic material and, thus, leads to significantly smaller effective electromechanical coupling coefficient k(15) and piezoelectric stress constant e(15) when compared to the piezoceramic fibre properties. However, it is found that the piezoelectric charge constant d(15) is less affected by the softer layers required by the MFC packaging.

Effect of fibre morphology on flocculation of fibre-cement suspensions

The objective of the present research was to evaluate the effect of fibre morphology (e.g., length, width, fibrillation, broken ends, content of fines and number of fibres per gram) on flocculation and drainage properties of fibre-cement suspensions and on physical properties of the fibre-cement composites. Mechanical refining was used to change the morphological properties of Eucalyptus and Pinus pulps. Results show that the mechanical refining increased the size of the formed flocs and decreased the concentration of free small particles (with dimensions between 1 and 20 pm) as a consequence of the increased fibrillation and content of fines, which increased the capacity of the fibres to capture the mineral particles. High levels of refining were necessary for Pinus pulp to obtain cement retention values similar to those obtained by unrefined Eucalyptus pulp. This is due to the higher number of fibres per gram in Eucalyptus pulp than in Pinus pulp. Pulp refining improved the packing of the particles and, although decreased the drainage rate. it contributed to a less porous structure, which improved the microstructure of the composite. (C) 2009 Elsevier Ltd. All rights reserved.