Growth of single-walled carbon nanotubes with controlled diameters and lengths by an aerosol method

On the basis of combined study of the transmission electron microscopy, scanning electron microscopy, Raman spectroscopy and ultraviolet–visible–near infrared absorption spectroscopy, the properties of the single-walled carbon nanotubes (SWCNTs), synthesized by aerosol (floating catalyst) chemical vapor deposition method by ferrocene vapor decomposition in the presence of carbon monoxide, are studied in details. The results show that increasing the temperature gives rise to the formation of high quality and large diameter SWCNTs. By monitoring the water-cooled probe position, both the bundle length and the diameter of the SWCNTs are effectively tuned due to the variation of the residence time and temperature profile in the reactor. An introduction of a small amount of CO₂ suppresses the growth of small diameter nanotubes and enlarges the mean diameter of SWCNT samples. The mean diameter of SWCNTs could be easily altered in a broad range from 1.1 to 1.9 nm during growth, which is essential for the SWCNT applications in optical and electronic devices.     

Phosphorus‐containing soybean‐oil copolymers: Cross‐metathesis of fatty acid derivatives as an alternative to phosphorus‐containing reactive flame retardants

Two different approaches to the creation of phosphorus‐containing soybean‐oil copolymers were investigated. First, two phosphorus‐containing styrene (ST) derivatives, diphenyl styryl phosphine oxide and dimethyl‐p‐vinylbenzylphosphonate (STP2), where tested as comonomers in the cationic copolymerization of soybean oil (SOY), ST, and divinylbenzene (DVB), to obtain heterogeneous systems in all cases. To overcome this drawback, the cross‐metathesis reaction of methyl 10‐undecenoate and STP2 was carried out to link the phosphorus moiety to the vegetable‐oil derivative. This second approach permitted the synthesis of a new reactive phosphorus‐containing plant‐oil derivative, which was incorporated into the soybean oil, ST, and DVB system. The cationic copolymerization was investigated, and the structure, thermal stability, and mechanical and flame‐retardant properties of the resulting copolymers were studied. Thermosets with moderate glass‐transition temperatures were obtained; this showed that the cross‐metathesis reaction is a convenient way to produce oil‐compatible monomers able to undergo homogeneous polymerization reactions. The resulting thermosets with 1% phosphorus had limiting oxygen index values about 24.0; this indicated an improvement in the fire‐retardant properties of the soybean‐oil‐based copolymers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Diaminofuroxan: Synthetic Approaches and Computer‐Aided Study of Thermodynamic Stability

Different approaches to synthesize diaminofuroxan are presented herein. Mathematical and quantum chemical methods were used to study the possible reasons for failures in the syntheses of diaminofuroxan. Additionally, structural isomers of this compound were generated. With the help of the results of quantum chemical calculations at levels of DFT B3LYP 6‐31G(d) and MP2 6‐31G(d), screening of the most stable isomeric forms in the gaseous phase and in water was performed. It was shown that diaminofuroxan is not the thermodynamically most stable isomer among its structural analogues.     

Renewable polybenzoxazines based in diphenolic acid

The reaction of mixtures of renewable diphenolic acid (DPA) and its methylesterbenzoxazine derivative (MDP-Bz) has been studied. The DPA was introduced to lower the high temperature needed to complete the curing of the pure benzoxazine. In this way, samples with different DPA/MDP-Bz ratio (0, 2, 5, 10 and 25% of DPA) were investigated. Moreover, high performance flame retardant thermosetting resins with phosphorus were prepared through the mixture of MDP-Bz and a DPA-phosphazene derivative (DPA-PPZ). The curing behavior of these materials was studied by differential scanning calorimetry (DSC). Finally, the properties of the materials were evaluated by termogravimetric analysis (TGA), dynamic mechanical analysis (DMTA), tensile measurements, limiting oxygen index (LOI) and UL-94 Burn Test.     

Styrene-butadiene branched star-shaped asphalt modifiers: Synthesis and mechanical characterization

Abstract

The synthesis and the corresponding characterization of styrene-butadiene (SB), branched, star-shaped copolymers was investigated as part of a research project on asphalt modification using polymers with precise molecular structures. The method of anionic polymerization was followed to prepare samples of block copolymers of SB, a synthesis method that controls chain-architecture, molecular weight distribution, monomer distribution, and the average molecular weight. The research studies are the synthesis of block copolymers including linear, three- and four-arms constructs, depending on the coupling agent used. The techniques of nuclear magnetic resonance (1NMR), differential scanning calorimetry (DSC), gel permeation chromatography (GPC), and rheology were carried out to characterize the copolymers. From the results of the 1NMR, DSC, and GPC analyses, all star-shaped copolymers investigated showed a similar block copolymer composition. Furthermore, the rheological behavior of one of the synthesized star-shaped copolymers was nearly the same as a four-branched commercial copolymer. Rheologically, the four-arm block copolymer sample had the largest storage modulus (G′) among the branched copolymers synthetized, indicating that such architecture produces a highly structured material. In regard to polymer-modified asphalt formulations, the three-branched copolymer architecture yielded better elastic behavior than the four-branch version. In summary, the findings of this investigation provide new insight about a polymer system that may offer advantages in industrial asphalt paving applications.     

UV-induced Persulfate Oxidation of Organic Micropollutants in Water Matrices

ABSTRACT

The efficacies of UV photolysis, UV-activated persulfate (UV/PS), and combined UV/Fe²⁺-activated persulfate (UV/PS/Fe²⁺) systems for degrading of different organic micropollutants in ultrapure water and groundwater were examined and compared. The studied micropollutants belonging to the different classes involved an artificial sweetener acesulfame K (ACE), beta-lactam antibiotic amoxicillin (AMX), and endocrine disrupting compound 4-nonylphenol (NP). Among the studied systems, the UV/PS/Fe²⁺ process showed the highest performance both in degradation and in mineralization of ACE (UVA-induced systems; k_app = 0.126 1/min and 80.3% TOC removal) and AMX (UVC-induced systems; k_app = 1.383 1/min and 85.4% TOC removal), followed by the UV/PS process. In the case of NP trials, the application of UVC/PS systems was the most promising, and after careful adjustment of oxidant concentration, it demonstrated a considerable improvement in the target compound degradation (at a NP/PS molar ratio of 1/4 k_app = 0.024 1/min) compared with the UVC photolysis (k_app = 0.016 1/min). Irrespective of the applied UV-induced treatment process, the efficacy of target compounds degradation was lower in groundwater as compared with ultrapure water trials.     

Static fatigue of Hi-Nicalon™-S fiber at elevated temperature in air,steam, and silicic acid-saturated steam

A facility for testing SiC fiber tows in static fatigue and creep at elevated temperatures in air and steam was developed. Static fatigue of Hi-Nicalon™-S fibers was investigated at 800°C-1100°C at applied stresses between 115 and 1250 MPa in air, in Si(OH)₄(g)-saturated steam, and in unsaturated steam. Fibers tested in Si(OH)₄(g)-saturated steam and in air had silica scales throughout the test sections, but those tested in unsaturated steam did not develop scales near the steam injection point. Fiber lifetimes in static fatigue were shortest in unsaturated steam, intermediate in Si(OH)₄(g)-saturated steam, and longest in air. Failure strains did not exceed 0.3%. Steady-state strain rates and static fatigue lifetimes are modelled empirically by the Monkman-Grant relationship. Failure mechanisms are discussed.     

Impact of A134 and E218 Amino Acid Residues of Tropomyosin on Its Flexibility and Function

Tropomyosin (Tpm) is one of the major actin-binding proteins that play a crucial role in the regulation of muscle contraction. The flexibility of the Tpm molecule is believed to be vital for its functioning, although its role and significance are under discussion. We choose two sites of the Tpm molecule that presumably have high flexibility and stabilized them with the A134L or E218L substitutions. Applying differential scanning calorimetry (DSC), molecular dynamics (MD), co-sedimentation, trypsin digestion, and in vitro motility assay, we characterized the properties of Tpm molecules with these substitutions. The A134L mutation prevented proteolysis of Tpm molecule by trypsin, and both substitutions increased the thermal stability of Tpm and its bending stiffness estimated from MD simulation. None of these mutations affected the primary binding of Tpm to F-actin; still, both of them increased the thermal stability of the actin-Tpm complex and maximal sliding velocity of regulated thin filaments in vitro at a saturating Ca²⁺ concentration. However, the mutations differently affected the Ca²⁺ sensitivity of the sliding velocity and pulling force produced by myosin heads. The data suggest that both regions of instability are essential for correct regulation and fine-tuning of Ca²⁺-dependent interaction of myosin heads with F-actin.     

Tissue-Specific Ferritin- and GFP-Based Genetic Vectors Visualize Neurons by MRI in the Intact and Post-Ischemic Rat Brain

(1) Background: Neurogenesis is considered to be a potential brain repair mechanism and is enhanced in stroke. It is difficult to reconstruct the neurogenesis process only from the histological sections taken from different animals at different stages of brain damage and restoration. Study of neurogenesis would greatly benefit from development of tissue-specific visualization probes. (2) Purpose: The study aimed to explore if overexpression of ferritin, a nontoxic iron-binding protein, under a doublecortin promoter can be used for non-invasive visualization of neurogenesis using magnetic resonance imaging (MRI). (3) Methods: Ferritin heavy chain (FerrH) was expressed in the adeno-associated viral backbone (AAV) under the doublecortin promoter (pDCX), specific for young neurons, in the viral construct AAV-pDCX-FerrH. Expression of the enhanced green fluorescent protein (eGFP) was used as an expression control (AAV-pDCX-eGFP). The viral vectors or phosphate-buffered saline (PBS) were injected intracerebrally into 18 adult male Sprague–Dawley rats. Three days before injection, rats underwent transient middle-cerebral-artery occlusion or sham operation. Animals were subjected to In vivo MRI study before surgery and on days 7, 14, 21, and 28 days after injection using a Bruker BioSpec 11.7 T scanner. Brain sections obtained on day 28 after injection were immunostained for ferritin, young (DCX) and mature (NeuN) neurons, and activated microglia/macrophages (CD68). Additionally, RT-PCR was performed to confirm ferritin expression. (4) Results: T2* images in post-ischemic brains of animals injected with AAV-pDCX-FerrH showed two distinct zones of MRI signal hypointensity in the ipsilesioned hemisphere starting from 14 days after viral injection—in the ischemic lesion and near the lateral ventricle and subventricular zone (SVZ). In sham-operated animals, only one zone of hypointensity near the lateral ventricle and SVZ was revealed. Immunochemistry showed that ferritin-expressing cells in ischemic lesions were macrophages (88.1%), while ferritin-expressing cells near the lateral ventricle in animals both after ischemia and sham operation were mostly mature (55.7% and 61.8%, respectively) and young (30.6% and 7.1%, respectively) neurons. RT-PCR confirmed upregulated expression of ferritin in the caudoputamen and corpus callosum. Surprisingly, in animals injected with AAV-pDCX-eGFP we similarly observed two zones of hypointensity on T2* images. Cellular studies also showed the presence of mature (81.5%) and young neurons (6.1%) near the lateral ventricle in both postischemic and sham-operated animals, while macrophages in ischemic lesions were ferritin-positive (98.2%). (5) Conclusion: Ferritin overexpression induced by injection of AAV-pDCX-FerrH was detected by MRI using T2*-weighted images, which was confirmed by immunochemistry showing ferritin in young and mature neurons. Expression of eGFP also caused a comparable reduced MR signal intensity in T2*-weighted images. Additional studies are needed to investigate the potential and tissue-specific features of the use of eGFP and ferritin expression in MRI studies.