Improved infrared spectroscopic method for the analysis of degree of N-deacetylation of chitosan

Various infrared spectroscopic techniques for the analysis of degree of N-deacetylation of chitosan were evaluated for accuracy. A new method was proposed which involved development of a calibration curve using the absorbance intensities of the chitosan infrared spectrum at 1655 and 3450 cm⁻¹. The degree of N-deacetylation of various chitosan samples was then determined by using the absorption ratios [A₁₆₅₅/A₃₄₅₀] in the equation of the calibration curve. This method yielded results which were superior to those of any of the previously reported infrared spectroscopic methods tested herein. Received: 27 March 1997/Revised: 16 May 1997/Accepted: 22 May 1997     

Flexural and tensile moduli of polypropylene nanocomposites and comparison of experimental data to Halpin‐Tsai and Tandon‐Weng models

This research focuses on the reinforcing efficiency of nanomateterials and the role of the reinforcement's dispersion and orientation on the nanocomposite's flexural and tensile moduli. Polypropylene‐based composites reinforced with (i) exfoliated graphite nanoplatelets, xGnP?, (ii) vapor grown carbon fibers, (iii) PAN‐based carbon fibers, (iv) highly structured carbon black and (v) montmorillonite clay were fabricated by extrusion and injection molding. It was found that graphite platelets are the best reinforcement in terms of flexural modulus whereas PAN‐based carbon fibers cause the largest improvement in the tensile modulus. The difference in the reinforcing efficiency during the flexural and tensile testing is attributed to (i) the degree of fiber alignment along the flow direction during injection molding, which is higher in the thinner tensile specimens than in the flex specimens; and (ii) the different deformation modes of the two tests. The importance of good dispersion of the reinforcements within the polymer matrix and of perfect contact between the two phases is emphasized comparing the experimental modulus data to theoretical predictions made using the Halpin‐Tsai and the Tandon‐Weng models. POLYM. ENG. SCI., 47:1796–1803, 2007. © 2007 Society of Plastics Engineers     

Fiber-Matrix Interfacial Adhesion Improvement in Carbon Fiber-Bisphenol-A Polycarbonate Composites by Polymer Grafting

Fiber-matrix interfacial adhesion in thermoplastic composites is generally poor due to the lack of formation of strong covalent and/or ionic bonds between the generally inert thermoplastic resins and the surface of the reinforcing fiber. Adhesion can be improved by forming covalent linkages between the fiber and the matrix by grafting a polymer of appropriate compatibility, molecular weight, and sufficient density onto the surface of the fiber. We have grafted low molecular weight polycarbonate and polymethyl methacrylates onto the surface of carbon fibers and measured an improvement in the level of adhesion ranging from 25% to100% over the ungrafted composites. It was also observed that the level of improvement in adhesion appears to be independent of the molecular weight of the grafted polymer. Examination of the fracture surface of these composites reveals that the failure is cohesive in the matrix for the polymer grafted fiber composites, while it is adhesive for the ungrafted composites.     

Reductive alkylation of illinois No. 6 coal. 1H and 13C n.m.r. spectra of the 13C-enriched alkylation products

The reductive alkylation of Illinois No. 6 coal has been carried out using potassium and naphthalene in tetrahydrofuran and methyl-¹³C and butyl-1 -¹³C iodides to alkylate the resultant polyanion. The soluble products of the reductive alkylation reaction were isolated by extraction and chromatography. Proton and carbon n.m.r. spectra were recorded. The intense resonance signal at δ3.95 which appears in the proton n.m.r. spectra of Illinois No. 6 coal butylated with unenriched butyl iodide is split into a doublet by the ¹³C nuclei. Similar results were obtained for the methylation products. The chemical shift and coupling interaction establish that aryl ethers are a very important constituent of the alkylated coal. The carbon n.m.r. spectra of the coal alkylated with ¹³C-enriched alkyl iodides are intense. The resonances of the C-alkylation products appear in a single broad band with a maximum intensity in spectral regions compatible with the formation of the reductive alkylation products of certain polynuclear aromatic hydrocarbons or the base-catalysed alkylation of certain benzylic carbon atoms. The resonances of the N -alkylation products appear in two distinct bands. These resonances are tentatively assigned to amines produced as a result of reductive alkylation of heterocyclic compounds. The resonances of the 0-alkylation products appear in three distinct bands which can be assigned to alkyl aryl ethers, alkyl aryl ethers with substituents at the adjacent positions, and to alkyl carboxylates. The ratio of ethers to carboxylates in the soluble alkylation products was determined to be 7.8 for butylation and 8.0 for methylation. The Chromatographic fractions contain different amounts of C-, N-, and 0-alkylation products. This finding suggests that the coal structure is not highly uniform.     

Fuel properties and emissions of soybean oil esters as diesel fuel

The effects of using blends of methyl and isopropyl esters of soybean oil with No. 2 diesel fuel were studied at several steady-state operating conditions in a four-cylinder turbocharged diesel engine. Fuel blends that contained 20, 50, and 70% methyl soyate and 20 and 50% isopropyl soyate were tested. Fuel properties, such as cetane number, also were investigated. Both methyl and isopropyl esters provided significant reductions in particulate emissions compared with No. 2 diesel fuel. A blend of 50% methyl ester and 50% No. 2 diesel fuel provided a reduction of 37% in the carbon portion of the particulates and 25% in the total particulates. The 50% blend of isopropyl ester and 50% No. 2 diesel fuel gave a 55% reduction in carbon and a 28% reduction in total particulate emissions. Emissions of carbon monoxide and unburned hydrocarbons also were reduced significantly. Oxides of nitrogen increased by 12%.     

Solid state magnetic resonance spectra of Illinois No. 6 coal and some reductive alkylation products

Illinois No. 6 coal and its reductive methylation and butylation products have been studied by magnetic resonance techniques. Conventional CP-MAS¹³Cn.m.r. spectroscopy indicates that 62% of the carbon atoms in the coal are aromatic and that about 6% of the carbon atoms are carbonyl. Esters are more abundant than carboxylic acids. The resonances of methoxy groups and other novel etheric carbon atoms are apparent in the high field region. Dipolar dephasing experiments suggest that methyl carbon atoms constitute no more than 16% of the carbon, methylene and methine carbon atoms about 14% and quaternary aliphatic carbon atoms about 2%. The dipolar dephasing experiments in conjunction with previous work also permit estimates of the hydrogen atom distribution. The THF-insoluble products obtained in the reductive alkylation reactions with¹³C-enriched alkylating agents contain paramagnetic and ferromagnetic substances that adversely influence the solid state n.m.r. spectra. However, good ¹³C n.m.r. spectra were obtained after these substances were extracted with aqueous hydrochloric acid. The O:C alkylation ratios are 1.2 and 1.0 for methylation and butylation, respectively. Dipolar dephasing experiments establish that the decay constants of functional groups in the whole coal and of C- and O-methyl-¹³C and C- and O-butyl-1 -¹³C nuclei in the labelled coal molecules are very similar to those of reference compounds. These findings suggest that the decay constants measured for the ¹³C nuclei in coals and coal-derived solids provide reliable information about their degree of substitution.     

Response to walnut olfactory and visual cues by the parasitic wasp Diachasmimorpha juglandis

Diachasmimorpha juglandis is a specialist parasitoid attacking fly larvae in the genus Rhagoletis that feed exclusively on walnut fruit husks. In a free-foraging assay comparing response to uninfested, infested, and mechanically damaged fruits, we first determined that D. juglandis use host feeding damage on the fruit as a cue for host presence. In another free-foraging assay that used artificial walnut models and wind tunnel experiments, D. juglandis distinguished infested from uninfested fruits by using either olfactory or visual cues separately. However, the response rate of wasps in the wind tunnel was raised considerably when visual cues were also available. We analyzed the volatile compounds emitted by cohorts of uninfested, mechanically damaged, and infested fruits 1, 3, 5, 8, and 10 days after oviposition by flies into the infested fruits. Total volatile emissions did not differ significantly among treatments, but quantitative changes in volatiles distinguished infested fruits from uninfested and damaged fruits. The fact that parasitoids did not distinguish between infested and damaged fruits in assays where damage was visible indicates that they rely on visual cues when those are available.     

Intercalation and exfoliation of clay nanoplatelets in epoxy‐based nanocomposites: TEM and XRD observations

Diglycidyl ether of bisphenol A (DGEBA) and diglycidyl ether of bisphenol F (DGEBF) reinforced with organo‐montmorillonite clay nanoplatelets were investigated using anhydride‐ and amine‐curing agents. The sonication technique was used to process epoxy/clay nanocomposites. The basal spacing of clay nanoplatelets was observed by wide‐angle X‐ray scattering (WAXS), small‐angle X‐ray scattering (SAXS) techniques, and transmission electron microscopy. It was found that the basal spacing of clay nanoplatelets in epoxy matrix was expanded after mixing with either DGEBA/DGEBF or methyltetrahydrophthalic‐anhydride (MTHPA) curing agent. The sonication technique provided larger d‐spacing of clay nanoplatelets. Because of the different curing temperatures, MTHPA‐cured epoxy/clay nanocomposites produced more expanded d‐spacing of clay nanoplatelets modified with methyl, tallow, bis(2‐hydroxyethyl) quaternary ammonium (MT2EtOH) than triethylenetetramine‐cured nanocomposites. Depending on the selection of curing agent and organic modification for clay nanoplatelets, the d‐spacing was expanded to be up to 8.72 nm. POLYM. ENG. SCI., 46:452–463, 2006. © 2006 Society of Plastics Engineers     

Isolation and characterization of ganglioside 9-O-acetyl-GD3 from bovine buttermilk

Bovine buttermilk contains a unique ganglioside, 9-O-acetyl-GD₃. In order to isolate large quantities of this ganglioside, a simplified isolation scheme which consists of several ion-exchange and silica gel column chromatographic procedures was devised. The isolated 9-O-acetyl-GD₃ was characterized on the basis of its thin-layer chromatographic behavior, its immunoreactivity with a specific monoclonal antibody, JONES, and by conversion to authentic GD₃ by mild base treatment.     

Electrophilic Aromatic Functionalization of Phenolic Photoresist Polymers

Summary Functionalization of both linear poly(4-hydroxystyrene) (PHS) and branched poly(4-hydroxystyrene) (PHS-B) was accomplished via a Reimer-Tiemann electrophilic aromatic substitution reaction. Linear and branched poly(4-hydroxystyrene-co-5-vinylsalicylaldehyde) (pHS/5VSA and pHS-B/5VSA) copolymers were observed to undergo acid-catalyzed, novolac type self-crosslinking. Both the pHS/5VSA and pHS-B/5VSA copolymer systems possessed a lower deep ultra violet microlithographic sensitivity compared to linear PHS when formulated in negative photoresists. The sluggishness of the negative photoresists containing 5-vinylsalicylaldehyde functionalized copolymers was attributed to a combination of resonance stabilization and steric hindrance effects.