Polyconductivity in polypyrrole: The correlated electron gas

p-toluensulfonate doped polypyrrole (PPy), undergoes an electric-field induced reversible transition from an insulating state to a highly conductive one. The spatially average field can be as small as 200 V/cm, when the temperature of the sample is below 20 K. The applied electric field leads to a sharp jump in the value of the current to a value which is nearly five orders of magnitude higher than before. When the applied electric field is reduced to below a critical value, the system switches back to a low conductive state. The effect is reversible, symmetric in voltage, and reproducible for different samples. The switching is, we believe, an electronic glass melting transition and it is due to the disordered, highly charged granular nature of PPy.

Single-step extraction of fluconazole from plasma by ultra-filtration for the measurement of its free concentration by high performance liquid chromatography.

High performance liquid chromatography (HPLC) is the reference method for measuring concentrations of antimicrobials in blood. This technique requires careful sample preparation. Protocols using organic solvents and/or solid extraction phases are time consuming and entail several manipulations, which can lead to partial loss of the determined compound and increased analytical variability. Moreover, to obtain sufficient material for analysis, at least 1 ml of plasma is required. This constraint makes it difficult to determine drug levels when blood sample volumes are limited. However, drugs with low plasma-protein binding can be reliably extracted from plasma by ultra-filtration with a minimal loss due to the protein-bound fraction. This study validated a single-step ultra-filtration method for extracting fluconazole (FLC), a first-line antifungal agent with a weak plasma-protein binding, from plasma to determine its concentration by HPLC. Spiked FLC standards and unknowns were prepared in human and rat plasma. Samples (240 microl) were transferred into disposable microtube filtration units containing cellulose or polysulfone filters with a 5 kDa cut-off. After centrifugation for 60 min at 15000g, FLC concentrations were measured by direct injection of the filtrate into the HPLC. Using cellulose filters, low molecular weight proteins were eluted early in the chromatogram and well separated from FLC that eluted at 8.40 min as a sharp single peak. In contrast, with polysulfone filters several additional peaks interfering with the FLC peak were observed. Moreover, the FLC recovery using cellulose filters compared to polysulfone filters was higher and had a better reproducibility. Cellulose filters were therefore used for the subsequent validation procedure. The quantification limit was 0.195 mgl(-1). Standard curves with a quadratic regression coefficient > or = 0.9999 were obtained in the concentration range of 0.195-100 mgl(-1). The inter and intra-run accuracies and precisions over the clinically relevant concentration range, 1.875-60 mgl(-1), fell well within the +/-15% variation recommended by the current guidelines for the validation of analytical methods. Furthermore, no analytical interference was observed with commonly used antibiotics, antifungals, antivirals and immunosuppressive agents. Ultra-filtration of plasma with cellulose filters permits the extraction of FLC from small volumes (240 microl). The determination of FLC concentrations by HPLC after this single-step procedure is selective, precise and accurate.

Hypoinsulinaemia, glucose intolerance and diminished beta-cell size in S6K1-deficient mice.

Insulin controls glucose homeostasis by regulating glucose use in peripheral tissues, and its own production and secretion in pancreatic beta cells. These responses are largely mediated downstream of the insulin receptor substrates, IRS-1 and IRS-2 (refs 4-8), through distinct signalling pathways. Although a number of effectors of these pathways have been identified, their roles in mediating glucose homeostasis are poorly defined. Here we show that mice deficient for S6 kinase 1, an effector of the phosphatidylinositide-3-OH kinase signalling pathway, are hypoinsulinaemic and glucose intolerant. Whereas insulin resistance is not observed in isolated muscle, such mice exhibit a sharp reduction in glucose-induced insulin secretion and in pancreatic insulin content. This is not due to a lesion in glucose sensing or insulin production, but to a reduction in pancreatic endocrine mass, which is accounted for by a selective decrease in beta-cell size. The observed phenotype closely parallels those of preclinical type 2 diabetes mellitus, in which malnutrition-induced hypoinsulinaemia predisposes individuals to glucose intolerance.

Stable isotope geochemistry and phase-equilibria of coesite-bearing whiteschists, Dora Maira massif, Western Alps

Peak metamorphic temperatures for the coesite-pyrope-bearing whiteschists from the Dora Maira Massif, western Alps were determined with oxygen isotope thermometry. The deltaO-18(SMOW) values of the quartz (after coesite) (delta O-18 = 8.1 to 8.6 parts per thousand, n = 6), phengite (6.2 to 6.4 parts per thousand, n = 3), kyanite (6.1 parts per thousand, n = 2), garnet (5.5 to 5.8 parts per thousand, n = 9), ellenbergerite (6.3 parts per thousand, n = 1) and rutile (3.3. to 3.6 parts per thousand, n = 3) reflect isotopic equilibrium. Temperature estimates based on quartz-garnet-rutile fractionation are 700-750-degrees-C. Minimum pressures are 31-32 kb based on the pressure-sensitive reaction pyrope + coesite = kyanite + enstatite. In order to stabilize pyrope and coesite by the temperature-sensitive dehydration reaction talc + kyanite = pyrope + coesite + H2O, the a(H2O) must be reduced to 0.4-0.75 at 700 750-degrees-C. The reduced a(H2O) cannot be due to dilution by CO2, as pyrope is not stable at X (CO2) > 0.02 (T = 750-degrees-C; P = 30 kb). In the absence of a more exotic fluid diluent (e.g. CH4 or N2), a melt phase is required. Granite solidus temperatures are approximately 680-degrees-C/30 kb at a(H2O) = 1.0 and are calculated to be approximately 70-degrees-C higher at a(H2O) = 0.7, consistent with this hypothesis. Kyanite-jadeite-quartz bands may represent a relict melt phase. Peak P-T-f(H2O) estimates for the whiteschist are 34 +/- 2 kb, 700-750-degrees-C and 0.4-0.75. The oxygen isotope fractionation between quartz (deltaO-18 = 11.6%.) and garnet (deltaO-18 = 8.7 parts per thousand) in the surrounding orthognesiss is identical to that in the coesite-bearing unit, suggesting that the two units shared a common, final metamorphic history. Hydrogen isotope measurements were made on primary talc and phengite (deltaD(smow) = -27 to -32 parts per thousand), on secondary talc and chlorite after pyrope (deltaD = - 39 to - 44 parts per thousand) and on the surrounding biotite (deltaD = -64 parts per thousand) and phengite (deltaD = -44 parts per thousand) gneiss. All phases appear to be in near-equilibrium. The very high deltaD values for the primary hydrous phases is consistent with an initial oceanic-derived/connate fluid source. The fluid source for the retrograde talc + chlorite after pyrope may be fluids evolved locally during retrograde melt crystallization. The similar deltaD, but dissimilar deltaO-18 values of the coesite-bearing whiteschists and hosting orthogneiss suggest that the two were in hydrogen isotope equilibrium, but not oxygen isotope equilibrium. The unusual hydrogen and oxygen isotope compositions of the coesite-bearing unit can be explained as the result of metasomatism from slab-derived fluids at depth.

A cryptic heterogametic transition revealed by sex-linked DNA markers in Palearctic green toads.

In sharp contrast to birds and mammals, most cold-blooded vertebrates have homomorphic (morphologically undifferentiated) sex chromosomes. This might result either from recurrent X-Y recombination (occurring e.g. during occasional events of sex reversal) or from frequent turnovers (during which sex-determining genes are overthrown by new autosomal mutations). Evidence for turnovers is indeed mounting in fish, but very few have so far been documented in amphibians, possibly because of practical difficulties in identifying sex chromosomes. Female heterogamety (ZW) has long been established in Bufo bufo, based on sex reversal and crossing experiments. Here, we investigate a sex-linked marker identified from a laboratory cross between Palearctic green toads (Bufo viridis subgroup). The F(1) offspring produced by a female Bufo balearicus and a male Bufo siculus were phenotypically sexed, displaying an even sex ratio. A sex-specific marker detected in highly reproducible AFLP genotypes was cloned. Sequencing revealed a noncoding, microsatellite-containing fragment. Reamplification and genotyping of families of this and a reciprocal cross showed B. siculus to be male heterogametic (XY) and suggested the same system for B. balearicus. Our results thus reveal a cryptic heterogametic transition within bufonid frogs and help explain patterns of hybrid fitness within the B. viridis subgroup. Turnovers of genetic sex-determination systems may be more frequent in amphibians than previously thought and thus contribute to the prevalence of homomorphic sex chromosomes in this group.

Bending modes of DNA directly addressed by cryo-electron microscopy of DNA minicircles.

We use cryo-electron microscopy (cryo-EM) to study the 3D shapes of 94-bp-long DNA minicircles and address the question of whether cyclization of such short DNA molecules necessitates the formation of sharp, localized kinks in DNA or whether the necessary bending can be redistributed and accomplished within the limits of the elastic, standard model of DNA flexibility. By comparing the shapes of covalently closed, nicked and gapped DNA minicircles, we conclude that 94-bp-long covalently closed and nicked DNA minicircles do not show sharp kinks while gapped DNA molecules, containing very flexible single-stranded regions, do show sharp kinks. We corroborate the results of cryo-EM studies by using Bal31 nuclease to probe for the existence of kinks in 94-bp-long minicircles.

Field Measurements of Ice Scraping Loads on Front Mounted Plow Blades, HR-374, 1997

Removal of ice from roads is of the more challenging task in winter highway maintenance. The best mechanical method is to use a truck with underbody plow blade, but such equipment is not available to all agencies charged with winter maintenance operations. While counties and cities often use motor graders to scrape ice, it would be of great benefit if front mounted plows could be used effectively for ice removal. To reveal and understand the factors that influence the performance of these plows, measurement of the forces experienced by the plow blades during ice scraping is desirable. This study explores the possibility of using accelerometers to determine the forces on a front-mounted plow when scraping ice. The plow was modeled by using a dynamic approach. The forces on the plow were to be determined by the measurement of the accelerations of the plow. Field tests were conducted using an "as is" front-mounted plow instrumented with accelerometers. The results of the field tests indicate that in terms of ice removal, the front-mounted plow is not favorable equipment. The major problem in this study is that the front mounted plow was not able to cut ice, and therefore experienced no significant scraping forces. However, the use of accelerometers seems to be promising for analyzing the vibration problems of the front-mounted plow.

Field Measurements of Plow Loads During Ice Removal Operations, HR-334, 1993

One of the more severe winter hazards is ice or compacted snow on roadways. While three methods are typically used to combat ice (salting, sanding and scraping), relatively little effort has been applied to improve methods of scraping ice from roads. In this project, a new test facility has been developed, comprising a truck with an underbody blade, which has been instrumented such that the forces to scrape ice from a pavement can be measured. A test site has been used, which is not accessible to the public, and ice covers have been sprayed onto the pavement and subsequently scraped from it, while the scraping loads have been recorded. Three different cutting edges have been tested for their ice scraping efficiency. Two of the blades are standard (one with a carbide insert, the other without) while the third blade was designed under the SHRP H-204A project. Results from the tests allowed two parameters to be identified. The first is the scraping efficiency which is the ratio of vertical to horizontal force. The lower this ratio, the more efficiently ice is being removed. The second parameter is the scraping effectiveness, which is related (in some as yet unspecified manner) to the horizontal load. The higher the horizontal load, the more ice is being scraped. The ideal case is thus to have as high a horizontal load as possible, combined with the lowest possible vertical load. Results indicate that the SHRP blade removed ice more effectively than the other two blades under equivalent conditions, and furthermore, did so with greater efficiency and thus more control. Furthermore, blade angles close to 0 deg provide for the most efficient scraping for all three blades. The study has shown that field testing of plow blades is possible in controlled situations, and that blades can be evaluated using this system. The system is available for further tests as are deemed appropriate.

Catalogue of Mesozoic radiolarian genera. Part 2: Jurassic-Cretaceous

The catalogue of Mesozoic radiolarian genera is a revision of all described genera with re-illustration of their type species. This project was organized under the auspices of the International Association of Radiolarian Paleontologists (Inter-Rad), and was carried out by the Mesozoic Working Group. This is the second of two contributions, this one devoted to the Jurassic-Cretaceous period. It contains 581 genera with re-illustration of their type species. This part shares 30 genera in common with the Triassic catalogue, most of which arose in the Carnian, Norian and Rhaetian. The sharp difference manifested between the Triassic fauna and the Jurassic-Cretaceous fauna is so evident that it justifies two independent catalogues. A comparable division between the Jurassic and Cretaceous could not be justified however, because of the similarity of the fauna, and by the greater number of genera crossing the Jurassic-Cretaceous boundary which is three times that for the Triassic-Jurassic boundary. A distinct characteristic of Jurassic-Cretaceous genera is the high number of nomina dubia (up to 131), contrary to the low number in the Triassic interval. This reflects, in part, the influence of Haeckelian taxonomy in earlier research on Jurassic-Cretaceous faunas prior to the application of SEM techniques. The Mesozoic Working Group has carefully reviewed and re-examined the taxonomy of all available genera, their family assignment and stratigraphic ranges. Following careful comparisons, 91 genera were declared as synonyms. The review has noted 26 homonyms which were duly notified to their corresponding authors, and were corrected previous to the publication of this catalogue. In spite of this effort, unfortunately nine homonyms still remain. Two invalid nominal genera, and two nomina nuda are also reported. The systematic revisions have validated 341 genera for the Jurassic-Cretaceous interval. At the end of this catalogue 24 additional are resented as support for those genera having a poor photographs p original illustration of the type species.

Measurement of Ice Scraping Forces on Snow-Plow Underbody Blades, HR-372, 1997

In this study, several new cutting edges for removal of ice from the roadway were tested in a series of closed road tests. These new cutting edges consisted of a variety of serrated shapes. The study also included measurement of ice scraping forces by in-service trucks. These trucks were instrumented in a similar manner as the truck used in the closed-road tests. Results from the closed-road and in-service tests were analyzed by two parameters. The first parameter is the scraping effectiveness, which is defined as the average horizontal force experienced by a cutting edge. The amount of ice scraped from the roadway is directly proportional to the magnitude of the scraping effectiveness. Thus an increase in scraping effectiveness indicates an increase in the amount of ice being scraped from the roadway. The second parameter is force angle, which is defined as tan to the -1 power [vertical force/horizontal force]. A combination of a minimal force angle and a maximized scraping effectiveness represents a case in which the maximal amount of ice is being removed from the pavement without an exceptionally large vertical force. Results indicate that each cutting edge produced a maximal scraping effectiveness with a testing configuration of a 15 deg blade angle and a 23,000 lb. download force. Results also indicate that each cutting edge produced a minimal force angle with a testing configuration of a 15 deg blade angle and a 10,000 lb. download force. Results from the in-service trucks produced similar data and also similar trends within the data when compared to the results of the closed-road tests. This result is most important, as it suggests that the closed-road tests do provide an accurate measure of ice scraping forces for a given blade and configuration of that blade. Thus if the closed-road tests indicate that certain blades perform well, there is now excellent reason to conduct full scale tests of such blades.

Preventing Cracking at Diaphragm/Plate Girder Connections in Steel Bridges, HR-393, 1998

Some of the Iowa Department of Transportation (Iowa DOT) continuous, steel, welded plate girder bridges have developed web cracking in the negative moment regions at the diaphragm connection plates. The cracks are due to out-of-plane bending of the web near the top flange of the girder. The out-of-plane bending occurs in the "web-gap", which is the portion of the girder web between (1) the top of the fillet welds attaching the diaphragm connection plate to the web and (2) the fillet welds attaching the flange to the web. A literature search indicated that four retrofit techniques have been suggested by other researchers to prevent or control this type of cracking. To eliminate the problem in new bridges, AASHTO specifications require a positive attachment between the connection plate and the top (tension) flange. Applying this requirement to existing bridges is expensive and difficult. The Iowa DOT has relied primarily on the hole-drilling technique to prevent crack extension once cracking has occurred; however, the literature indicates that hole-drilling alone may not be entirely effective in preventing crack extension. The objective of this research was to investigate experimentally a method proposed by the Iowa DOT to prevent cracking at the diaphragm/plate girder connection in steel bridges with X-type or K-type diaphragms. The method consists of loosening the bolts at some connections between the diaphragm diagonals and the connection plates. The investigation included selecting and testing five bridges: three with X-type diaphragms and two with K-type diaphragms. During 1996 and 1997, these bridges were instrumented using strain gages and displacement transducers to obtain the response at various locations before and after implementing the method. Bridges were subjected to loaded test trucks traveling in different lanes with speeds varying from crawl speed to 65 mph (104 km/h) to determine the effectiveness of the proposed method. The results of the study show that the effect of out-of-plane loading was confined to widths of approximately 4 in. (100 mm) on either side of the connection plates. Further, they demonstrate that the stresses in gaps with drilled holes were higher than those in gaps without cracks, implying that the drilling hole technique is not sufficient to prevent crack extension. The behavior of the web gaps in X-type diaphragm bridges was greatly enhanced by the proposed method as the stress range and out-of-plane distortion were reduced by at least 42% at the exterior girders. For bridges with K-type diaphragms, a similar trend was obtained. However, the stress range increased in one of the web gaps after implementing the proposed method. Other design aspects (wind, stability of compression flange, and lateral distribution of loads) must be considered when deciding whether to adopt the proposed method. Considering the results of this investigation, the proposed method can be implemented for X-type diaphragm bridges. Further research is recommended for K-type diaphragm bridges.

Physiological changes during postharvest senescence of broccoli

The objective of this work was to determine the early physiological changes throughout shelf life of fresh broccoli (Brassica oleracea L. var. italica) cv. Piracicaba Precoce at 25ºC and relative humidity of 96% in the dark until complete senescence. Head inflorescences showed lack of turgidity and commercial value when weight loss reached up to 5%, coinciding with 48 hour after harvest. Chlorophyll content was stable until 24 hours after harvesting; afterwards, an intense degradation phase took place. At 72 hours, total head yellowing was observed when chlorophyll content dropped to 30% of its initial content. Peroxidase activity increased by 1.4 fold during the first six hours, dropping to its lowest level approximately 24 hours after harvesting. However, from this time on, an increment of activity was observed until 72 hours. At 24 hours after harvesting, respiration was reduced by 50%. At later stages of senescence, respiration of florets was stable, but in a lower level than that determined at harvest. Sharp reduction of starch and reducing sugars was observed within 24 hours after harvesting, followed by continuous period of decline in starch and non-reducing sugars.

Non-contact microdrilling of mouse zona pellucida with an objective-delivered 1.48-microns diode laser.

BACKGROUND and OBJECTIVE: A non-touch laser-induced microdrilling procedure is studied on mouse zona pellucida (ZP). STUDY DESIGN/MATERIALS and METHODS: A 1.48-microns diode laser beam is focused in a 8-microns spot through a 45x objective of an inverted microscope. Mouse zygotes, suspended in a culture medium, are microdrilled by exposing their ZP to a short laser irradiation and allowed to develop in vitro. RESULTS: Various sharp-edged holes can be generated in the ZP with a single laser irradiation. Sizes can be varied by changing irradiation time (3-100 ms) or laser power (22-55 mW). Drilled zygotes present no signs of thermal damage under light and scanning electron microscopy and develop as expected in vitro, except for a distinct eight-shaped hatching behavior. CONCLUSION: The microdrilling procedure can generate standardized holes in mouse ZP, without any visible side effects. The hole formation can be explained by a local photothermolysis of the protein matrix.

Smart instrumentation for determination of ligament stiffness and ligament balance in total knee arthroplasty.

Ligament balance is an important and subjective task performed during total knee arthroplasty (TKA) procedure. For this reason, it is desirable to develop instruments to quantitatively assess the soft-tissue balance since excessive imbalance can accelerate prosthesis wear and lead to early surgical revision. The instrumented distractor proposed in this study can assist surgeons on performing ligament balance by measuring the distraction gap and applied load. Also the device allows the determination of the ligament stiffness which can contribute a better understanding of the intrinsic mechanical behavior of the knee joint. Instrumentation of the device involved the use of hall-sensors for measuring the distractor displacement and strain gauges to transduce the force. The sensors were calibrated and tested to demonstrate their suitability for surgical use. Results show the distraction gap can be measured reliably with 0.1mm accuracy and the distractive loads could be assessed with an accuracy in the range of 4N. These characteristics are consistent with those have been proposed, in this work, for a device that could assist on performing ligament balance while permitting surgeons evaluation based on his experience. Preliminary results from in vitro tests were in accordance with expected stiffness values for medial collateral ligament (MCL) and lateral collateral ligament (LCL).

Radiographic total disc replacement angle measurement accuracy using the Oxford Cobbometer: precision and bias.

Total disc replacement (TDR) clinical success has been reported to be related to the residual motion of the operated level. Thus, accurate measurement of TDR range of motion (ROM) is of utmost importance. One commonly used tool in measuring ROM is the Oxford Cobbometer. Little is known however on its accuracy (precision and bias) in measuring TDR angles. The aim of this study was to assess the ability of the Cobbometer to accurately measure radiographic TDR angles. An anatomically accurate synthetic L4-L5 motion segment was instrumented with a CHARITE artificial disc. The TDR angle and anatomical position between L4 and L5 was fixed to prohibit motion while the motion segment was radiographically imaged in various degrees of rotation and elevation, representing a sample of possible patient placement positions. An experienced observer made ten readings of the TDR angle using the Cobbometer at each different position. The Cobbometer readings were analyzed to determine measurement accuracy at each position. Furthermore, analysis of variance was used to study rotation and elevation of the motion segment as treatment factors. Cobbometer TDR angle measurements were most accurate (highest precision and lowest bias) at the centered position (95.5%), which placed the TDR directly inline with the x-ray beam source without any rotation. In contrast, the lowest accuracy (75.2%) was observed in the most rotated and off-centered view. A difference as high as 4 degrees between readings at any individual position, and as high as 6 degrees between all the positions was observed. Furthermore, the Cobbometer was unable to detect the expected trend in TDR angle projection with changing position. Although the Cobbometer has been reported to be reliable in different clinical applications, it lacks the needed accuracy to measure TDR angles and ROM. More accurate ROM measurement methods need to be developed to help surgeons and researchers assess radiological success of TDRs.