Synthesis and Characterization of Organotin Polyesters Derived from 3,5-Pyridinedicarboxylic Acid

Organotin polyesters were synthesized from the interfacial condensation of organotin dihalides and salts of 3,5-pyridinedicarboxylic acid. The polymers are synthesized in moderate to high yields and are moderate to high polymers. MALDI MS, IR spectral, and NMR spectral results are consistent with the proposed structure. The Sn–O stretching band is found at about 1,028 cm^?1. Infrared spectra are consistent with majority of the products having a non-bridged structure about the tin. All of the polymers exhibit some inhibition of two pancreatic cancer cell lines. The dibutyltin and dicyclohexyltin products show sufficiently good inhibition of both cell lines as to merit further testing.     

Design and testing of a functional arm orthosis in patients with neuromuscular diseases.

The objective of this study was to determine the utility of a passive gravity-balanced arm orthosis, the Wilmington robotic exoskeleton (WREX), for patients with neuromuscular diseases. The WREX, a four-degrees-of-freedom functional orthosis, is energized by rubber bands to eliminate gravity and is attached to the wheelchair. The development and clinical testing of WREX is described in this report. Seventeen patients (14 boys and 3 girls) with muscular disabilities participated in the study. Ages ranged from 4 to 20 years. Criteria for inclusion included a weakened arm, use of a wheelchair, the ability to grasp and release objects, and the ability to provide feedback on device use. Testing consisted of administering the Jebsen test of hand function without WREX and then testing again after approximately two weeks of wearing the WREX orthosis. The timed results of each task within the test then were compared. Specific tasks related to vertical movement required less time to perform with the WREX. A large number of subjects were able to perform the Jebsen tasks with the WREX, where they were unable to perform the task without the WREX. Patients can benefit from WREX because it increases their performance in daily living activities and makes many tasks possible. The range-of-motion in the patients' arms increased considerably, while the time required to complete some of the Jebsen test tasks decreased. Most patients were very receptive to WREX, although a few were ambivalent.     

Comprehensive Proteomic Analysis of Spider Dragline Silk from Black Widows: A Recipe to Build Synthetic Silk Fibers

The outstanding material properties of spider dragline silk fibers have been attributed to two spidroins, major ampullate spidroins 1 and 2 (MaSp1 and MaSp2). Although dragline silk fibers have been treated with different chemical solvents to elucidate the relationship between protein structure and fiber mechanics, there has not been a comprehensive proteomic analysis of the major ampullate (MA) gland, its spinning dope, and dragline silk using a wide range of chaotropic agents, inorganic salts, and fluorinated alcohols to elucidate their complete molecular constituents. In these studies, we perform in-solution tryptic digestions of solubilized MA glands, spinning dope and dragline silk fibers using five different solvents, followed by nano liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) analysis with an Orbitrap Fusion™ Tribrid™. To improve protein identification, we employed three different tryptic peptide fragmentation modes, which included collision-induced dissociation (CID), electron transfer dissociation (ETD), and high energy collision dissociation (HCD) to discover proteins involved in the silk assembly pathway and silk fiber. In addition to MaSp1 and MaSp2, we confirmed the presence of a third spidroin, aciniform spidroin 1 (AcSp1), widely recognized as the major constituent of wrapping silk, as a product of dragline silk. Our findings also reveal that MA glands, spinning dope, and dragline silk contain at least seven common proteins: three members of the Cysteine-Rich Protein Family (CRP1, CRP2 and CRP4), cysteine-rich secretory protein 3 (CRISP3), fasciclin and two uncharacterized proteins. In summary, this study provides a proteomic blueprint to construct synthetic silk fibers that most closely mimic natural fibers.     

Lignin‐based polyurethane doped with carbon nanotubes for sensor applications

Modified eucalyptus kraft lignin doped with multiwall carbon nanotubes (MWCNTs) was used as a macromonomer in step‐growth polymerization with tolylene 2,4‐diisocyanate terminated poly(propylene glycol) with the aim of producing a conductive copolymer for all‐solid‐state potentiometric chemical sensor applications. The crosslinked elastomeric polyurethane obtained was characterized by Fourier transform infrared attenuated total reflection spectroscopy, scanning electron microscopy, tunnelling electron microscopy and atomic force microscopy. Doping of lignin‐based polyurethane with MWCNTs produced a significant enhancement of its electrical conductivity without deterioration of thermal and viscoelastic properties. The polymer composite displayed a low percolation threshold at an MWCNT concentration of 0.18% (w/w), which was explained by the oriented distribution of MWCNTs along lignin clusters. All lignin‐based polyurethanes doped with MWCNTs at concentrations above the percolation threshold are suitable for sensor applications. Copyright © 2012 Society of Chemical Industry     

Career experiences of doctors of psychology.

Surveyed 184 graduates (mean age 37 yrs) of 9 PsyD programs to determine the professional activities in which they were engaged, satisfaction with careers and graduate training in professional psychology, and public acceptance of the PsyD degree and compared the results with similar data on PhD clinicians. Most Ss were primarily engaged in direct professional services in professional settings. They were generally satisfied with their careers in professional psychology and significantly more satisfied with the graduate training they had received than were clinical psychologists trained in traditional PhD programs. More Ss reported that the PsyD degree was an advantage rather than a disadvantage when competing for jobs with candidates who had other degrees. PsyD Ss were found to be active joiners of professional associations. 91% of PsyD Ss who applied for licensure or certification encountered no difficulty due to their degree. Almost no unfavorable attitudes toward the degree were perceived among clients, employers, or colleagues. It is concluded that fears about perception of the PsyD as a second-rate credential are unfounded. (8 ref) (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Direct numerical simulation of turbulent channel flows using a stabilized finite element method

Direct numerical simulations (DNS) of incompressible turbulent channel flows at Re_τ = 180 and 395 (i.e., Reynolds number, based on the friction velocity and channel half-width) were performed using a stabilized finite element method (FEM). These simulations have been motivated by the fact that the use of stabilized finite element methods for DNS and LES is fairly recent and thus the question of how accurately these methods capture the wide range of scales in a turbulent flow remains open. To help address this question, we present converged results of turbulent channel flows under statistical equilibrium in terms of mean velocity, mean shear stresses, root mean square velocity fluctuations, autocorrelation coefficients, one-dimensional energy spectra and balances of the transport equation for turbulent kinetic energy. These results are consistent with previously published DNS results based on a pseudo-spectral method, thereby demonstrating the accuracy of the stabilized FEM for turbulence simulations.     

Phosphorus limits phytoplankton growth on the Louisiana shelf during the period of hypoxia formation

The Louisiana shelf is the largest zone of seasonally oxygen-depleted coastal bottom water in the U.S. This condition results from the high freshwater and nutrient input from the Mississippi River and the resulting high primary productivity in the river plume. The hypoxic zone has doubled in area since regular measurements began in 1985. Identification of the nutrient(s) limiting phytoplankton growth on the shelf and their sources is important for developing hypoxia-reduction strategies; nitrogen (N) has been considered the most important to date. In this study, we measured multiple parameters addressing nutrient limitation or stress (nutrient concentrations and ratios, alkaline phosphatase activity, phosphorus (P)turnover times, and changes in chlorophyll a concentrations in nutrient enrichment bioassays) in the Mississippi River plume in March, May, July, and September of 2001. All results indicate that phytoplankton growth on the Louisiana shelf was limited by P in May and July of 2001. P limitation was weakly evident in March, but N was limiting in September. The observed P limitation in spring and summer probably results from the historical increases in riverine N due to excessive N loading and has potential implications for developing hypoxia reduction strategies.     

Increased reach and effectiveness of a statewide tobacco quitline after the addition of access to free nicotine replacement therapy

Background

Tobacco users receiving behavioural and pharmacological assistance are more likely to quit. Although telephone quitlines provide population access to counselling, few offer pharmacotherapy.

Objective

To assess change in cessation rates and programme impact after the addition of free nicotine replacement therapy (NRT) to statewide quitline services.

Design, setting, participants

An observational study of cohorts of callers to the Minnesota QUITPLAN^SM Helpline before (n  =  380) and after (n  =  373) the addition of access to free NRT.

Intervention

Mailing of NRT (patch or gum) to callers enrolling in multi‐session counselling.

Main outcome measure

Thirty‐day abstinence six months after programme registration.

Results

The number of callers increased from 155 (SD 75) to 679 (180) per month pre‐NRT to post‐NRT (difference 524, 95% confidence interval (CI) 323 to 725). Post‐NRT, the proportion of callers enrolling in multi‐session counselling (23.4% v 90.1%, difference 66.6%, 95% CI 60.8% to 71.6%) and using pharmacotherapy (46.8% v 86.8%, difference 40.0%, 95% CI 31.3% to 47.9%) increased. Thirty‐day abstinence at six months increased from 10.0% pre‐NRT to 18.2% post‐NRT (difference 8.2%, 95% CI 3.1% to 13.4%). Post‐NRT the average number of new ex‐smokers per month among registrants increased from 15.5 to 123.6 (difference 108.1, 95% CI 61.1 to 155.0). The cost per quit pre‐NRT was $1362 (SD $207). The cost per quit post‐NRT was $1934 ($215) suggesting a possible increase in cost per quit (difference $572, 95% CI −$12 to $1157).

Conclusion

The addition of free NRT to a state quitline is followed by increases in participation and abstinence rates resulting in an eightfold increase in programme impact. These findings support the addition of access to pharmacological therapy as part of state quitline services.