Self-assembly of nanoparticle-rich interphases in fiber reinforced polymeric composites using migrating agents

Thermoplastic additives, known as migrating agents, can be added to nanoparticle loaded thermosetting resins to form self-assembled nanoparticle structures. Most notably, in fiber reinforced thermosetting composites, self-assembled nanoparticle rich fiber-matrix interphases can be formed. While the self-assembly mechanism remains unclear, depletion interaction correctly describes the types of self-assembled structures formed. Formulations containing modest concentrations of migrating agent form self-assembled fiber-matrix interphases without causing aggregation in the bulk. Slight overdoses of migrating agent can lead to the formation of nanoparticle aggregates in the bulk phase, which can ultimately reduce the mechanical properties of the composite. Even larger overdoses of migrating agent cause the formation of large and open nanoparticle aggregates, indicative of rapid aggregation. Depletion theory predicts that larger molecular weight migrating agents should induce greater attractive forces, thus reducing the concentrations required to form these self-assembled structures. In this study, the migrating agent molecular weight dependence on the self-assembly and aggregation phenomenon are investigated. As predicted by depletion theory, larger molecular weights led to the formation of self-assembled interphases and aggregates at lower concentrations.     

An Atomistic Understanding of Allosteric Inhibition of Glutamate Racemase: a Dampening of Native Activation Dynamics

Glutamate racemases (GR) are members of the family of bacterial enzymes known as cofactor-independent racemases and epimerases and catalyze the stereoinversion of glutamate. D-amino acids are universally important for the proper construction of viable bacterial cell walls, and thus have been repeatedly validated as attractive targets for novel antimicrobial drug design. Significant aspects of the mechanism of this challenging stereoinversion remain unknown. The current study employs a combination of MD and QM/MM computational approaches to show that the GR from H. pylori must proceed via a pre-activation step, which is dependent on the enzyme's flexibility. This mechanism is starkly different from previously proposed mechanisms. These findings have immediate pharmaceutical relevance, as the H. pylori GR enzyme is a very attractive allosteric drug target. The results presented in this study offer a distinctly novel understanding of how AstraZeneca's lead series of inhibitors cripple the H. pylori GR's native motions, via prevention of this critical chemical pre-activation step. Our experimental studies, using SPR, fluorescence and NMR WaterLOGSY, show that H. pylori GR is not inhibited by the uncompetitive mechanism originally put forward by Lundqvist et al.. The current study supports a deep connection between native enzyme motions and chemical reactivity, which has strong relevance to the field of allosteric drug discovery.     

Effect of temperature and pH on the post-mortem degradation of myofibrillar proteins

Incubation of bovine muscle at 37°C promoted a more drastic proteolytic change in myofibrillar proteins, as determined from sodium dodecyl sulphate polyacrylamide gels of isolated myofibrils, than incubation at 4°C. Degradation of myosin and troponin-T were the most noticeable changes at 37°C. Loss of α-actinin was observed in the 4°C incubated muscle. Ground bovine muscle incubated at pH 5·4 and 7 revealed that alterations in myosin and troponin-T were the most noticeable changes at ph 5·4 while troponin-T and α-actinin were altered at pH7. More troponin-T degradation occurred at pH 5·4 and 37°C than at pH7 and 4°C (similar to the degradation of myosin), indicating that troponin-T degradation in post-mortem muscle may be an indicator of overall myofibrillar proteolysis and not responsible for post-mortem tenderisation per se. Myosin degradation in the ground samples incubated at pH 5·4 and in whole samples incubated at 37°C was compared with the digestion of myofibrillar myosin by papain. Both pyrophosphate and Guba-Straub extracts of the 37°C and pH 5·4 treated samples confirmed that myosin degradation did occur to a much greater extent at this temperature and pH than at 4°C and pH7, and, in addition, at pH 5·4 frequent cleavage occurred near the papain sensitive site of myosin.     

Critical incidents in counseling psychology professionals' and trainees' social justice orientation development.

Through a qualitative, critical incident research design, this study identified and defined critical incidents that cultivated a social justice orientation among counseling psychology doctoral students and professionals. Research questions included: (a) What incidents are critical in the development of a social justice orientation? (b) Of these incidents, which are most influential? (c) How do these incidents affect social justice orientation development? Thirty-six counseling psychology doctoral students and professionals, who demonstrated a commitment to social justice through scholarship and clinical practice, completed an online survey, which consisted of rank-order and open-ended items. Qualitative data were analyzed utilizing the constant comparative method. Analyses revealed five categories of critical incidents to which participants attributed their social justice orientation development. In addition, five themes were identified that categorized the ways in which critical incidents changed individuals. Analyses of rank-ordered items indicated that the categories of Exposure to Injustice and Influence of Significant Persons were most frequently ranked as the most influential critical incidents in the development of a social justice orientation. Implications of these results and future directions for education, training, and research are discussed. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Editorial

Editorial Introduction

Editorial     

A Preliminary Study of the Toxicological Properties of Selected Polymer–Ferrocene Conjugates

Prompted by early observations of the cytotoxic and antineoplastic properties of certain ferrocene and ferricenium derivatives, efforts in this laboratory were focused on the synthesis of carrier-bound ferrocene compounds. Subsequent cell culture tests carried out with selected conjugates obtained in that program showed these polymers to be highly active antiproliferative agents. In the present project toxicological work has been performed in vivo on several ferrocene conjugates in an effort to assess their toxic effects in experimental animals (CD-1 mice). The conjugates, all based on an ,-DL-polyaspartamide backbone structure, comprise the ferrocene drug model as a terminal on short side chains containing biofissionable amide or ester links for intracellular drug release. The polymers, dissolved in phosphate-buffered saline, have been injected in predetermined concentrations into the vein of the mice, and the maximum tolerated dose (MTD) levels have been determined, the latter referring to the highest dose levels administered that would allow long-term survival of the test animals. For the five conjugates tested, MTD levels range from about 3 to 30 mg Fe/kg or 0.05–0.66 mmol Fe/kg. Compared on a molar metal-to-metal basis with similarly structured platinum conjugates tested previously (MTD, 0.14–2.66 mmol Pt/kg), these values are indicative of comparatively high toxicity of the ferrocene polymers. Some implications of these findings are discussed.     

Evidence for the presence of components of the alternative (properdin) pathway of complement activation in respiratory secretions

Activation of the alternative complement pathway by respiratory secretory IgA was demonstrated by incubating purified, aggregated preparations of serum and secretory IgA with neat human serum. No depletion of the early components (C1-4) was observed, but 63 and 70% of C3-9, respectively, were consumed. The C3-9-consuming capacity of heat-aggregated nasal secretions from an IgA-deficient volunteer was compared with heat-aggregated nasal secretions from a normal volunteer known to have secretory IgA. The deficient secretions consumed C3-9, whereas the IgA deficient secretions did not. Reconstitution of the nasal secretions from the IgA-deficient volunteer with purified secretory IgA produced alternative pathway activation. Factor B of the alternative complement pathway was found to be present in 16 of 18 bronchoalveolar lavage samples (BALF) from normal volunteers. Simultaneous measurement of lavage and serum albumin and Factor B concentrations rendered it unlikely that Factor B was merely a transudative product from serum in half the samples but rather suggested that it may be a component of lower respiratory tract secretions. The presence of an intact alternative complement pathway in BALF was indicated by showing that cobra venom factor and endotoxin cleaved functionally pure human C3 when mixed with BALF, but had no effect on C3 in the absence of BALF.     

Attraction of a free-living nematode, Caenorhabditis elegans, to foodborne pathogenic bacteria and its potential as a vector of Salmonella poona for preharvest contamination of cantaloupe

Caenorhabditis elegans was studied to determine the potential role of free-living microbivorous nematodes as vectors for preharvest contamination of fruits and vegetables with foodborne pathogens. The propensity of C. elegans to be attracted to seven strains of Escherichia coli O157:H7, eight serotypes of Salmonella, six strains of Listeria monocytogenes, and cantaloupe juice was investigated. Twenty to 30 adult worms were placed on the surface of K agar midway between a 24-h bacterial colony and 10 microl of uninoculated tryptic soy broth (TSB) or cantaloupe juice positioned 1.5 cm apart. The numbers of nematodes that migrated to the colony, to the TSB, and to the cantaloupe juice within 5, 10, 15, and 20 min at 21 degrees C were determined, and then the plates were incubated at 37 degrees C for up to 7 days to determine the ability of C. elegans to survive and reproduce in bacterial colonies. The nematode was attracted to colonies of all test pathogens and survived and reproduced within colonies for up to 7 days. C. elegans was not attracted to cantaloupe juice. The potential of C. elegans to serve as a vector for the transport of Salmonella Poona to cantaloupe rinds was investigated. Adult worms that had been immersed in a suspension of Salmonella Poona were deposited 1 or 3 cm below the surface of soil on which a piece of cantaloupe rind was placed. The rind was analyzed for the presence of Salmonella Poona after 1, 3, 7, and 10 days at 21 degrees C. The presence of Salmonella Poona was evident more quickly on rinds positioned on soil beneath which C. elegans inoculated with Salmonella Poona was initially deposited than on rinds positioned on soil beneath which Salmonella Poona alone was deposited. The time required to detect Salmonella Poona on rinds was longer when the rind was placed 3 cm above the inoculum than when the rind was placed 1 cm above the inoculum. Free-living nematodes may play a role in the preharvest dispersal of incidental human pathogens in soil to the surfaces of raw fruits and vegetables in contact with soil during development and maturation, as evidenced by the behavior of C. elegans as a test model.     

High-spectral-resolution lidar with iodine-vapor filters: measurement of atmospheric-state and aerosol profiles

A high-spectral-resolution lidar can measure vertical profiles of atmospheric temperature, pressure, the aerosol backscatter ratio, and the aerosol extinction coefficient simultaneously. We describe a system with these characteristics. The transmitter is a narrow-band (FWHM of the order of 74 MHz), injection-seeded, pulsed, double YAG laser at 532 nm. Iodine-vapor filters in the detection system spectrally separate the molecular and aerosol scattering and greatly reduce the latter (-41 dB). Operating at a selected frequency to take advantage of two neighboring lines in vapor filters, one can obtain a sensitivity of the measured signal-to-air temperature ratio equal to 0.42%/K. Using a relatively modest size transmitter and receiver system (laser power times telescope aperture equals 0.19 Wm(2)), our measured temperature profiles (0.5-15 km) over 11 nights are in agreement with balloon soundings to within 2.0 K over an altitude range of 2-5 km. There is good agreement in the lapse rates, tropopause altitudes, and inversions. In principle, to invert the signal requires a known density at one altitude, but in practice it is convenient to also use a known temperature at that altitude. This is a scalable system for high spatial resolution of vertical temperature profiles in the troposphere and lower stratosphere, even in the presence of aerosols.