Kinetics of Polyurethane Formation in Polymerization Reactions Using the Organometallic Diol (η5-C5H4CH2CH2OH)2Mo2(CO)6

Summary The kinetics of the dibutyltin diacetate (DBTA) – catalyzed polymerization reactions of (η⁵-C₅H₄CH₂CH₂OH)₂Mo₂(CO)₆ with Hypol 2000 (an isocyanate-terminated polyether prepolymer) and with 1,4-butanediol were studied, as were the kinetics of a copolymerization involving (η⁵-C₅H₄CH₂CH₂OH)₂Mo₂(CO)₆ and PEG-1000 (a poly(ethylene glycol)) with Hypol 2000. The purpose was to determine if (η⁵-C₅H₄CH₂CH₂OH)₂Mo₂(CO)₆ appreciably affected the overall rate of the polymerization reaction and if it changed the mechanism of the reaction. The kinetics were analyzed with a fitting program, which allowed extraction of the rate constants for the individual elementary steps in the mechanism. The results showed that (η⁵-C₅H₄CH₂CH₂OH)₂Mo₂(CO)₆ does not significantly alter the timescale of the reaction and that the same reaction mechanism is likely used as with the 1,4-butanediol and PEG-1000. There are some differences in the rate constants of the elementary steps, but these differences can be attributed to the increased steric crowding caused by the bulkier (η⁵-C₅H₄CH₂CH₂OH)₂Mo₂(CO)₆ diol. The effect of the (η⁵-C₅H₄CH₂CH₂OH)₂Mo₂(CO)₆ on the polymers’ physical properties was also investigated. As is the case with other segmented polyurethanes, the hydrogen bonding index (HBI) and the relative amount of soft segments of the (η⁵-C₅H₄CH₂CH₂OH)₂Mo₂(CO)₆-containing polyurethane correlate in a general way with the physical properties of the polymer.     

Measuring aerosol size distributions with the aerodynamic aerosol classifier

The Aerodynamic Aerosol Classifier (AAC) is a novel instrument that selects aerosol particles based on their relaxation time or aerodynamic diameter. Additional theory and characterization is required to allow the AAC to accurately measure an aerosol’s aerodynamic size distribution by stepping while connected to a particle counter (such as a Condensation Particle Counter, CPC). To achieve this goal, this study characterized the AAC transfer function (from 32 nm to 3 μm) using tandem AACs and comparing the experimental results to the theoretical tandem deconvolution. These results show that the AAC transmission efficiency is 2.6–5.1 times higher than a combined Krypton-85 radioactive neutralizer and Differential Mobility Analyzer (DMA), as the AAC classifies particles independent of their charge state. However, the AAC transfer function is 1.3–1.9 times broader than predicted by theory. Using this characterized transfer function, the theory to measure an aerosol’s aerodynamic size distribution using an AAC and particle counter was developed. The transfer function characterization and stepping deconvolution were validated by comparing the size distribution measured with an AAC-CPC system against parallel measurements taken with a Scanning Mobility Particle Sizer (SMPS), CPC, and Electrical Low Pressure Impactor (ELPI). The effects of changing AAC classifier conditions on the particle selected were also investigated and found to be small (<1.5%) within its operating range.

Copyright © 2018 American Association for Aerosol Research     

Refractive index retrievals for polystyrene latex spheres in the spectral range 220–420 nm

The recent development of an Aerosol Extinction Differential Optical Absorption Spectrometer (AE-DOAS) has allowed for the retrieval of wavelength dependent complex refractive indices for polystyrene latex spheres (PSL). The AE-DOAS is a white-type multi-pass gas cell coupled to a UV-Vis spectrometer. Refractive index values are retrieved for wavelengths between 220 and 420 nm by minimizing the χ² goodness-of-fit between measured extinction for five diameters of PSL and model Mie Theory predictions. Comparison to literature shows agreement at wavelengths >360 nm demonstrating the validity of this new instrumental approach while expanding the known refractive index range for PSLs further into the UV where it is previously unreported. In the studied wavelength range, coefficients for the general Cauchy dispersion relationship (A = 1.538(11); B = 0.0043(16) μm²; C = 0.00094(5) μm⁴) for PSLs were determined using the retrieved real portion of the refractive index and the wavelength in microns. In addition, this work indicates that the precision of retrieved values is impacted by the particle diameters chosen for the experiment where retrievals for shorter wavelengths of light benefit from the study of smaller sized particles.

Copyright © 2017 American Association for Aerosol Research     

Cover Image,Volume 92, Issue 7

The cover image, by Aravindan Rajendran et al., is based on the Research Article Nutrient recovery from ethanol co‐products by a novel mycoalgae biofilm: attached cultures of symbiotic fungi and algae, DOI: 10.1002/jctb.5177 .

     

Toxicity of sodium nitrilotriacetate (NTA) to the fathead minnow and an amphipod in soft water

Amphipods, Gammarus pseudolimnaeus Bousfield and fathead minnows, Pimephales promelas Rafinesque, were submitted to acute (96-h) and chronic (generation-cycle) bioassays with sodium nitrilotriacetic acid (NTA). All measurements are reported as Na₃NTA. The average 96-h TL50 values under flow-through conditions were 98 mg 1⁻¹NTA for the amphipod and 114 mg 1⁻¹ for the fathead minnow. The acute toxicity of NTA was caused in part by the high pH resulting from the addition of large amounts of NTA (> 100 mg 1⁻¹) to soft water. Controlling pH reduced the lethality of NTA by at least one-half to fathead minnow larvae. The chronic no-effect level of NTA to the amphipods was 19 mg 1⁻¹; in fathead minnows, it exceeded the highest exposure level (> 54 mg 1⁻¹).     

Synthesis and characterization of potassium metal/graphitic carbon nanofiber intercalates

Direct reaction of herringbone, platelet, or narrow, tubular herringbone graphitic carbon nanofibers (GCNFs) with molten potassium gives K/GCNF intercalates with stoichiometric control of potassium loading. Intercalate formation is confirmed by powder X-ray diffraction and micro-Raman spectroscopy. K/GCNF intercalates act as radical-anion alkene polymerization catalysts and reduce water with stoichiometric formation of hydrogen gas. Stage-1 K/narrow, tubular GCNF intercalate exhibits thermionic emission at 300 degrees C. Stage-1 K/herringbone GCNF intercalate is an excellent thermionic emitter having high thermal stability up to 1000 degrees C. K/GCNF intercalates have much reduced work functions of ca. 2.2 eV with localized emission showing a work function of 1.6 eV.     

Bio‐Derived Polymers for Sustainable Lithium‐Ion Batteries

Biologically derived organic molecules are a cost‐effective and environmentally benign alternative to the widely used metal‐based electrodes employed in current energy storage technologies. Here, the first bio‐derived pendant polymer cathode for lithium‐ion batteries is reported. The redox moiety is flavin and is derived from riboflavin (vitamin B₂). A semi‐synthetic methodology is used to prepare the pendant polymer, which is composed of a poly(norbornene) backbone and pendant flavin units. This semi‐synthetic approach reduces the number of chemical transformations required to form this new functional material. Lithium‐ion batteries incorporating this polymer have a 125 mAh g^?1 capacity and an ≈2.5 V operating potential. It is found that charge transport is greatly improved by forming hierarchical structures of the polymer with carbon black, and new insight into electrode degradation mechanisms is provided which should be applicable to polymer electrodes in general. This work provides a foundation for the use of bio‐derived pendant polymers in sustainable, high‐performance lithium‐ion batteries.     

Estrogen-induced alterations in amh and dmrt1 expression signal for disruption in male sexual development in the zebrafish

Dmrt1 and amh are genes involved in vertebrate sex differentiation. In this study, we cloned dmrt1 and amh cDNAs in zebrafish (Danio rerio) and investigated the effects of exposure to 17a-ethinylestradiol (EE2), during early life on their patterns of expression and impact on the subsequent gonadal phenotype. Expression of both amh and dmrt1 in embryos was detected as early as at 1 day post fertilization (dpf) and enhanced expression of amh from 25 dpf was associated with the period of early gonadal differentiation. Sex-dependent differences in enhanced green fluorescent protein transgene expression driven by the promoter of the germ cell-specific vas gene were exploited to show that at 28dpf and 56dpf both amh and dmrt1 mRNA were overexpressed in males compared with females. Exposure during early life to environmentally relevant concentrations of EE2 had a suppressive effect on the expression of both amh and dmrt1 mRNAs and this was associated with a cessation/retardation in male gonadal sex development. Our findings indicate that estrogen-induced suppression in expression of dmrt1 and amh during early life correlate with subsequent disruptive effects on the sexual phenotype in males.     

Inverse scattering for frequency-scanned full-field optical coherence tomography

Full-field optical coherence tomography (OCT) is able to image an entire en face plane of scatterers simultaneously, but typically the focus is scanned through the volume to acquire three-dimensional structure. By solving the inverse scattering problem for full-field OCT, we show it is possible to computationally reconstruct a three-dimensional volume while the focus is fixed at one plane inside the sample. While a low-numerical-aperture (NA) OCT system can tolerate defocus because the depth of field is large, for high NA it is critical to correct for defocus. By deriving a solution to the inverse scattering problem for full-field OCT, we propose and simulate an algorithm that recovers object structure both inside and outside the depth of field, so that even for high NA the focus can be fixed at a particular plane within the sample without compromising resolution away from the focal plane.     

Neurofuzzy adaptive controlling of selective stimulation for FES: a case study.

A controller was designed for the selective stimulation of the sciatic nerve with a multiple contact cuff electrode to generate a desired torque in the ankle joint of cat. The design integrates three approaches, artificial neural network (ANN) modeling, fuzzy logical adaptation, and geometrical mapping. The geometrical mapping refers to the vector transformation from the joint coordinates to the virtual muscle coordinates which have been conceptually developed to represent the major recruitment features of contact-based functional units in the physical plant. This method reduces the complexity of generating a data set for training the neural network in the feedforward path and implementing the on-line learning algorithm embedded in the feedback loop. The controller was evaluated by computer simulation with the experimental data obtained from the torque generation in five acute cats. The results show that the ANN-based feedforward is capable of predicting 65% of a given desired isometric torque, and the fuzzy logical machine is able to provide suitable gains for feedback modulation to reduce the error from 35 to 8.5% and produce a robust control.