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The micro-optical ring electrode. 3: Transient photocurrent studies of photophysical-electrochemical and photophysical-chemical-electrochemical systems.

The micro-optical ring electrode (MORE) is a photoelectrochemical device based on a ring microelectrode that uses the insulating material interior to the ring electrode as a light guide. In this paper, we describe the preparation and characterization of very thin ring MOREs with (ring inner radius)/(ring outer radius) > 0.99. Theoretically, we derive asymptotic analytical expressions for the time dependence of the diffusion-limited transient light-on photocurrent generated by two general types of photoelectrochemical systems: (a) the PE (photophysical-electrochemical) system, wherein the photoexcited species itself is directly detected on the ring; (b) the PCE (photophysical-chemical-electrochemical) system, wherein the photoexcited species undergoes a homogeneous electron transfer reaction prior to electrochemical detection. Experimentally, we establish that it is possible to use such MOREs to study the wavelength dependence of photocurrents derived from photoelectrochemically active systems, such as the Ru(bipy)3 2+/Fe3+ PCE system, demonstrating the potential utility of the MORE as a selective electroanalytical probe. We also use our expressions for the time dependence of photocurrents at the MORE to derive values for the photoelectrochemical kinetic parameters of this system, including the rate coefficient for the back reaction of photogenerated Ru(bipy)3 3+ (0.115 s(-1)) and the quantum efficiency for the primary redox products, Ru(bipy)3 3+ and Fe2+, escaping cage recombination, phi(CE) = 0.099.

2,2'-Dipyridyl↗

Evaluation of pulse oximetry as a continuous monitoring technique in the neonatal intensive care unit.

We tested a number of pulse oximeters in a neonatal ICU to assess their performance as continuous monitors. Using a computer-based data acquisition system and a movement sensor, we determined the proportion of time that the oximeter was unreliable as the duration of monitored time that the oximeter heart rate (HR) differed from a "true" HR by greater than 10 beat/min using each of the oximeters in both their short and long averaging mode. The tested devices were found to be unreliable for 11.9% to 25% in the short averaging mode, and from 13.8% to 29% in the longer averaging mode. Most of the HR discrepancy was secondary to movement of the extremity. A newer model of one of the devices, which uses ECG R-wave detection to trigger optical pulse scanning, was associated with markedly reduced motion artifact (2.1% to 4.1%) when it accurately interpreted HR. The response of the devices to an acute loss of pulsation revealed differences in design and performance with some oximeters indicating zero saturation and others continuing to display a value while indicating a "low quality signal." Pulse oximeters are a valuable adjunct to clinical oxygen monitoring and, when properly applied and reliably indicating the infant's HR, will accurately reflect arterial saturation (r = .8, p less than .0001). ECG synchronization appears to reduce motion artifact when the ECG R-wave is detected.

Chronic Disease↗

Optical-based molecular imaging: contrast agents and potential medical applications.

Laser- and sensitive charge-coupled device technology together with advanced mathematical modelling of photon propagation in tissue has prompted the development of novel optical imaging technologies. Fast surface-weighted imaging modalities, such as fluorescence reflectance imaging (FRI) and 3D quantitative fluorescence-mediated tomography have now become available [1, 2]. These technical advances are paralleled by a rapid development of a whole range of new optical contrasting strategies, which are designed to generate molecular contrast within a living organism. The combination of both, technical advances of light detection and the refinement of optical contrast media, finally yields a new spectrum of tools for in vivo molecular diagnostics. Whereas the technical aspects of optical imaging are covered in more detail in a previous review article in "European Radiology" [3], this article focuses on new developments in optical contrasting strategies and design of optical contrast agents for in vivo diagnostics.

Animals↗

External-cavity wavelength tunable laser with an electro-optic deflector.

A near-IR tunable external-cavity laser that uses an electro-optic deflector and a reflection grating as a tunable filter is demonstrated. The deflector is an electronically reconfigurable nonpixelated nematic liquid-crystal device. By controlling the voltage applied to the electro-optic deflector, a tuning range of 12 nm and a side-mode suppression higher than 30 dB are obtained.

Journal Article↗

Surface plasmon polariton-based optical beam profiler.

We describe a surface plasmon polariton- (SPP-) based device for measuring the intensity distribution of strongly focused light beams. A gold thin film configured as a sharp step is positioned in the focal region of a light beam, converting light into SPPs. The SPPs emit directional leakage radiation into the glass substrate beneath the thin film. The intensity of the leakage radiation is proportional to the intensity of the incident local light at the position of the step, allowing us to reconstruct the optical field profile by scanning the thin film's edge through the focal region.

Journal Article↗

Analytic chemistry. Everyone's a (future) chemist.

The development of small, portable "lab-on-a-chip" devices has the potential to provide individuals with the tools for complex chemical and biochemical analysis. In his Perspective, Burns charts recent progress toward fabricating such devices. He highlights the report by Terray et al., who use latex spheres manipulated by optical traps to pump fluids. The integration of such components into larger, more complex devices will open up applications from airborne contaminant detection to genetic testing and screening.

Air Pollutants↗

Multivariate optimization of an axially-viewed inductively coupled plasma multichannel-based emission spectrometer for the analysis of environmental samples.

An experimental design procedure was applied to optimize the operating conditions of an axially-viewed inductively coupled plasma emission spectrometer instruments equipped with echelle optics with cross dispersion and charge transfer device. The multivariate effect of carrier gas flow rate and r.f. power on several analytical figures was investigated and discussed. Both ultrasonic and pneumatic nebulization were used. For the final choice of the optimum, different criteria were taken into account, mainly plasma robustness, instrumental precision, analyte and background net emission, detection limits and signal-to-background ratios. It was found that the use of moderate power (1100W) and mean carrier gas flow rate (0.75 L/min) allows to obtain sufficient plasma robustness, satisfactory precision, and excellent signal-to-background ratios and limits of detection, favorable for ultratrace element determinations in environmental matrices.

Fresh Water↗

Giant mitochondria in the retina cone inner segments of shrews of genus Sorex (Insectivora, Soricidae).

The retinas of three species of shrews (Sorex araneus, S. coronatus, and S. minutus) were analyzed. Two kinds of photoreceptors were identified according to (among other characteristics) the traits of the mitochondria of their inner segments. The rod inner segments contained several round or oval mitochondria distributed longitudinally inside the ellipsoid. The cone inner segment showed a few mitochondria, which we classified as megamitochondria (maximum length = 4.22 microm in S. araneus, 5.68 microm in S. coronatus, and 2.42 microm in S. minutus). An analysis of serial thin sections in S. coronatus showed that these large organelles occurred in the apical and central portions of the ellipsoid. In the peripheral and basal regions of the ellipsoid, megamitochondria were frequently accompanied by smaller mitochondria. The giant mitochondria were irregular in form and densely packed, and a reduced cytosol was observed between each mitochondria. In general, they exhibited an electron-dense matrix and a complex system of cristae, which varied in length and array. In mammalian retina, megamitochondria have only been described in the ellipsoid of the tree shrews Tupaia glis and T. belangeri, two diurnal Scandentia with a rich-cone retina. In general terms, Sorex megamitochondria are morphologically very similar to those reported for Tupaia, especially in their arrangement in the cone ellipsoid. However, they differ in the orientation of the cristae. We propose that the ellipsoid of Sorex may serve two functions: as a source of energy for receptor cells, and as a device for improving the cone outer segment optics.

Animals↗

Cranial surgery and navigation with a compact intraoperative MRI system.

Experience with a compact unit for intraoperative magnetic resonance imaging (iMRI) and integrated surgical navigation is presented. The system, commercially known as the PoleStar N-10 (Odin Medical Technologies, Yokne'am, Israel) includes a 0.12 Tesla permanent magnet that docks under a regular OR table. A passive infrared-based optical navigation system is included and the device can be controlled by the operating neurosurgeon and staff. We have operated on 93 patients using the PoleStar N-10. Diagnoses included glioma in 27, pituitary adenoma in 19, meningioma in 15, and others in 40. Lesions were removed from the skull base in 35 patients of whom 8 had posterior fossa masses. Surgery was affected by imaging in 51% of operations. Additional lesion, not otherwise apparent, was removed in 21; in 14 other patients unnecessary dissection was avoided when the new image confirmed that the surgical goals had been achieved. Additional time incurred with use of the PoleStar diminished with increasing experience. Testing of the navigation tool confirmed its accuracy to be comparable to other "frameless stereotactic" devices, on the order of 2 mm; likewise accuracy was increased by using T1 weighted imaging with thin slices. The introduction of new, faster imaging sequences and targeting tools has helped to make the PoleStar N-10 a routine tool for intracranial surgical navigation, with the added benefit of updated imaging during the procedure.

Adenoma↗

Chemical microanalytical systems: objectives and latest developments.

Chemical microanalysis systems are at a very early state of development. At the present time a modular approach with subsystems carrying out the various functions such as sampling, preparation and measurement seems to be favored by the developers. The marketpotential of the systems can be seen primarily in the area of inexpensive monitoring equipment for environmental and process control. Reduction of size leads also to smaller sample volumes, less waste and shorter analysis time: Miniaturization is in many cases an essential feature for biological and in-vivo medical investigations, while some properties inherently associated with miniaturization can also lead to substantial improvements in the technical performance of the microsystem as compared to its macro version. This will be demonstrated by discussing some microsystems which include spectroscopic detection systems:- Miniature separation instruments coupled with advanced miniaturized detection device based on photothermal spectroscopy- Integrated-optical NIR evanescent wave sensor systems- Optochemical and biosensor systems

Journal Article↗

Performance evaluation of salivary amylase activity monitor.

In order to quantify psychological stress and to distinguish eustress and distress, we have been investigating the establishment of a method that can quantify salivary amylase activity (SMA). Salivary glands not only act as amplifiers of a low level of norepinephrine, but also respond more quickly and sensitively to psychological stress than cortisol levels. Moreover, the time-course changes of the salivary amylase activity have a possibility to distinguish eustress and distress. Thus, salivary amylase activity can be utilized as an excellent index for psychological stress. However, in dry chemistry system, a method for quantification of the enzymatic activity still needs to be established that can provide with sufficient substrate in a testing tape as well as can control enzymatic reaction time. Moreover, it is necessary to develop a method that has the advantages of using saliva, such as ease of collection, rapidity of response, and able to use at any time. In order to establish an easy method to monitor the salivary amylase activity, a salivary transcription device was fabricated to control the enzymatic reaction time. A fabricated salivary amylase activity monitor consisted of three devices, the salivary transcription device, a testing-strip and an optical analyzer. By adding maltose as a competitive inhibitor to a substrate Ga1-G2-CNP, a broad-range activity testing-strip was fabricated that could measure the salivary amylase activity with a range of 0-200 kU/l within 150 s. The calibration curve of the monitor for the salivary amylase activity showed R2=0.941, indicating that it was possible to use this monitor for the analysis of the salivary amylase activity without the need to determine the salivary volume quantitatively. In order to evaluate the assay variability of the monitor, salivary amylase activity was measured using Kraepelin psychodiagnostic test as a psychological stressor. A significant difference of salivary amylase activity was recognized between the pre-stress and mid-stress periods. This study demonstrated that broad-range salivary amylase activity monitor was developed that could be used with only 5 microl of saliva.

Adult↗

Effect of incisional friction and ophthalmic viscosurgical devices on the heat generation of ultrasound during cataract surgery.

PURPOSE: To determine the thermal features of the Legacy (Alcon) and Sovereign (Advanced Medical Optics) phacoemulsification machines in a cadaver eye and with 7 ophthalmic viscosurgical devices (OVDs). SETTING: In situ and in vitro study. METHODS: Temperature without occlusion was recorded at the sleeve placed in the wound of a cadaver eye, and temperature over baseline was determined after 60 seconds. The result was then compared with the results in a previous study that used balanced salt solution (BSS) in artificial chambers. In the second portion of the experiment, with irrigation and aspiration lines occluded, temperature was recorded at the sleeve placed in an artificial chamber filled with sodium hyaluronate 2.3% (Healon5), sodium hyaluronate 1.4% (Healon GV), sodium hyaluronate 1.0% (Healon), sodium hyaluronate 1.6% (Amvisc Plus), sodium hyaluronate 1.0% (Provisc), sodium hyaluronate 3.0%-chondroitin sulfate 4.0% (Viscoat), or hyaluronate 3.0% (Vitrax). Temperature over baseline was also determined after 60 seconds. These results were compared with each set of OVD data and with the results in the prior BSS study. RESULTS: In the eye-bank model, the Legacy machine had a 62% temperature increase from incisional friction and the Sovereign machine had a decrease of 8.6% over results in an artificial anterior chamber. The OVD temperature increases were greater for the Sovereign (P<.001) and followed the same general trend for the Legacy. The least temperature increase was with Amvisc Plus, Healon, and Healon GV; the intermediate increases were with Provisc and Vitrax; and the greatest increases were with Viscoat and Healon5. The OVD findings did not correlate with viscosity or pseudoplasticity. CONCLUSIONS: Incisional friction alone increased heat generation in the Legacy, a stroke-length driven instrument, more than in the Sovereign, a power-driven instrument. Ophthalmic viscosurgical devices are not only a concern due to outflow occlusion but can also add up to 6 times the heat in comparison with BSS. The need to aspirate the OVD before using ultrasound is thus verified.

Aged↗

Robotic coronary artery bypass grafting (CABG)--the Leipzig experience.

Technical and anatomical limitations as well as human factors complicate endoscopic coronary bypass surgery. Computer-enhanced telemanipulation systems overcome some of these shortcomings by restoring the dexterity and precision of a distant operator (surgeon) within a confined space. Endoscopic coronary artery bypass grafting (CABG) has evolved from a merely experimental approach to a clinical concept. Although CABG was initially exclusively performed on the arrested heart, adjunct technologies such as endoscopic vacuum-assisted stabilizers now allow a closed-chest, beating-heart procedure. The development of anastomotic devices, and further refinements in telemanipulator technology, optical systems, and image-guided augmented-reality scenarios will greatly facilitate endoscopic bypass grafting in the future.

Coronary Artery Bypass↗

Generation of natural pH gradients in microfluidic channels for use in isoelectric focusing

As a part of an ongoing investigation of the use of isoelectric focusing (IEF) in microfluidic devices, pH gradients were electrochemically formed and optically quantified in microfluidic channels using acid-base indicators. The microchannels consisted of two parallel 40-mm-long electrodes with an interelectrode gap of 2.54 mm; top and bottom transparent windows were separated by 0.2 mm. Gradients in pH were formed as a result of the electrochemical decomposition of water at an applied potential not higher than 2.5 V to avoid generation of gas bubbles. Solutions contained low concentrations of a single buffer. The stability of the pH gradients and their sensitivity to changes in initial conditions were investigated under static (nonflow) conditions. Isoelectric focusing of sample biological analytes, bovine hemoglobin and bovine serum albumin, was performed to illustrate the potential of "microfluidic transverse IEF" for use in continuous concentration and separation systems.

Journal Article↗

Detector for liquid chromatography based on acoustic emissions from an oscillating flame.

The acoustic flame detector (AFD) is examined as a novel detector for liquid chromatography (LC). It is based upon the acoustic emission frequency of an oscillating hydrogen/oxygen premixed flame and produces a universal response toward organic molecules. A stable frequency near 1000 Hz, which further depends on mobile-phase composition, is achieved for flow rates in the microliter per minute range. The mass flow sensitivity of the AFD demonstrates a linear response over 3 orders of magnitude and a detection limit (S/sigma = 3) of approximately 15 ng of C/s for a series of alcohols. For cyclopentanol, this amounts to an injected mass of approximately 77 ng based on a 0.5-microL injection of a 196 ppm solution in methanol (flow rate 20 microL/min methanol; peak width 30 s). Similar sensitivity is observed using a water mobile phase. Low-frequency (1/f ) noise contributions are dominant with or without mobile phase present. The AFD demonstrates a uniform molar sensitivity toward carbon compounds independent of their optical properties or volatility. Results suggest the device might serve as a simple, inexpensive universal LC detector.

Journal Article↗

Adhesion kinetics of viable Cryptosporidium parvum oocysts to quartz surfaces.

The transport and deposition (adhesion) kinetics of viable Cryptosporidium parvum oocysts onto ultrapure quartz surfaces in a radial stagnation point flow system were investigated. Utilizing an optical microscope and an image-capturing device enabled real time observation of oocyst deposition behavior onto the quartz surface in solutions containing either monovalent (KCl) or divalent (CaCl2) salts. Results showed a significantly lower oocyst deposition rate in the presence of a monovalent salt compared to a divalent salt. With a monovalent salt, oocyst deposition rates and corresponding attachment efficiencies were relatively low, even at high KCl concentrations where Derjaguin-Landau-Verwey-Overbeek (DLVO) theory predicts the absence of an electrostatic energy barrier. On the other hand, in the presence of a divalent salt, oocyst deposition rates increased continuously as the salt concentration was increased over the entire range of ionic strengths investigated. The unusually low deposition rate in a monovalent salt solution is attributed to "electrosteric" repulsion between the Cryptosporidium oocyst and the quartz surface, most likely due to proteins on the oocyst surface that extend into the solution. It is further proposed that specific binding of calcium ions to the oocyst surface functional groups results in charge neutralization and conformational changes of surface proteins that significantly reduce electrosteric repulsion.

Animals↗

Multicolor photochromism of two- and three-component diarylethene crystals.

Novel photochromic single crystals composed of three different kinds of diarylethenes, 1,2-bis(3,5-dimethyl-2-thienyl)perfluorocyclopentene (1a), 1,2-bis(2,5-dimethyl-3-thienyl)perfluorocyclopentene (2a), and 1,2-bis(2-methyl-5-p-methoxyphenyl-3-thienyl)perfluorocyclopentene (3a), have been prepared. The three-component crystals turned yellow, orange, red, purple, blue, green, or black upon irradiation with light of appropriate wavelengths. The colors of the crystals were thermally stable in the dark and completely bleached by irradiation with visible light. Such multicolored photochromic crystals have potential for the application to optoelectronic devices, such as multifrequency three-dimensional optical memory media or full-color displays.

Journal Article↗

Generating suspended single-walled carbon nanotubes across a large surface area via patterning self-assembled catalyst-containing block copolymer thin films.

Using self-assembled block copolymers as templates, catalytically active nanostructures with controlled size and space have been produced. A self-assembled polystyrene-b-polyferrocenylsilane thin film and monolayer of surface micelles of cobalt-complexed polystyrene-b-poly(2-vinylpyridine) are fully compatible with novolac-based conventional photoresists. Combining bottom-up self-assembly of catalyst-containing block copolymers with top-down microfabrication processing, plateaus covered with arrays of catalytically active nanostructures have been generated. Spatially selective growth of suspended single-walled carbon nanotubes over a large surface area has been achieved. Greatly enhanced Raman signals have been detected from the suspended tubes. This facile method of creating highly ordered catalyst nanostructures on top of posts enables the rational synthesis of suspended carbon nanotubes, thus facilitating the study of CNT properties by optical methods and enabling the fabrication of devices based on suspended CNTs.

Letter↗