Crystal and molecular structures of 1-[3-(3,4-dimethoxyphenyl)-2-propenoyl]pyrrolidine.

The crystal structure of 1-[3-(3,4-dimethoxyphenyl)-2-propenoyl]pyrrolidine (C15H19NO3) (I) has been determined by X-ray analysis. It crystallizes orthorhombic space group Pbca with a = 24.295(3), b = 15.086(3), c = 7.552(3)A, V = 2768(1)A3, Z = 8, Dcalc = 1.254 g/cm3, mu = (Mo K(alpha)) = 0.87 cm(-1). The title compound has analgesic activity of cycloaliphatic amine part. The molecule is deviated from planar configuration.     

4-Transitivity and 6-figures in some Moufang-Klingenberg planes

In this paper, the Moufang-Klingenberg plane over a local alternative ring R of dual numbers is studied. It is shown that its collineation group is transitive on quadrangles. It is therefore shown that the coordinatization of these Moufang-Klingenberg planes is independent of the choice of the coordinatization quadrangle. Also, the concept of 6-figures is extended to these Moufang-Klingenberg planes and it is shown that any 6-figure corresponds to only one inversible m ∈ R.     

Synthesis and copolymerization of new phosphorus‐containing acrylates

Two phosphorus‐containing acrylate monomers were synthesized from the reaction of ethyl α‐chloromethyl acrylate and t‐butyl α‐bromomethyl acrylate with triethyl phosphite. The selective hydrolysis of the ethyl ester monomer with trimethylsilyl bromide (TMSBr) gave a phosphonic acid monomer. The attempted bulk polymerizations of the monomers at 57–60 °C with 2,2′‐azobisisobutyronitrile (AIBN) were unsuccessful; however, the monomers were copolymerized with methyl methacrylate (MMA) in bulk at 60 °C with AIBN. The resulting copolymers produced chars on burning, showing potential as flame‐retardant materials. Additionally, α‐(chloromethyl)acryloyl chloride (CMAC) was reacted with diethyl (hydroxymethyl)phosphonate to obtain a new monomer with identical ester and ether moieties. This monomer was hydrolyzed with TMSBr, homopolymerized, and copolymerized with MMA. The thermal stabilities of the copolymers increased with increasing amounts of the phosphonate monomer in the copolymers. A new route to highly reactive phosphorus‐containing acrylate monomers was developed. A new derivative of CMAC with mixed ester and ether groups was synthesized by substitution, first with diethyl (hydroxymethyl)phosphonate and then with sodium acetate. This monomer showed the highest reactivity and gave a crosslinked polymer. The incorporation of an ester group increased the rate of polymerization. The relative reactivities of the synthesized monomers in photopolymerizations were determined and compared with those of the other phosphorous‐containing acrylate monomers. Changing the monomer structure allowed control of the polymerization reactivity so that new phosphorus‐containing polymers with desirable properties could be obtained. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2207–2217, 2003     

Functionalization of saturated hydrocarbons. High temperature bromination of octahydropentalene. Part 19

The synthesis and thermal bromination of octahydropentalene was studied. The reaction afforded 1a,3a,4b,6b-tetrabromo-1,2,3,4,5,6-hexahydropentalene (14) with remarkable regio- and stereospecificity. The structure of the product was determined by ¹H and ¹³C NMR data and single X-ray structural analysis. The treatment of octahydropentalene with tenfold bromine gave the octabromopentalene derivative. The formation mechanism of the products is discussed.     

Effect of electrolyte on surface free energy components of feldspar minerals using thin-layer wicking method

Application of the thin-layer wicking (TLW) technique on powdered minerals is useful for characterizing their surfaces. Albite (Na-feldspar) and orthoclase (K-feldspar) are feldspar minerals which are frequently found in the same matrix. Despite similarities in their physicochemical properties, separation of these minerals from each other by flotation is generally possible in the presence of monovalent salts such as NaCl. Both albite and orthoclase exhibit the same microflotation properties and rather close electrokinetic profiles in the absence of salt. In this study, contact angles of albite and orthoclase determined by the TLW technique yielded close values in the absence and presence of amine collector. While the calculated surface energies and their components determined using contact angle data reveal that the energy terms remain farther apart in the absence of the collector, the differences narrow down at collector concentrations where full flotation recoveries are obtained. However, the effect of addition of NaCl on contact angles and surface free energy components at constant amine concentration indicates that albite is significantly affected by salt addition, whereas orthoclase remains marginally affected. This interesting finding is explained on the basis of ion-exchange properties, the stability of the interface, flotation data, and zeta potential data in the presence of NaCl.     

Ester derivatives of α-hydroxymethylacrylates: Itaconate isomers giving high molecular weight polymers

New ester derivatives of ethyl α-hydroxymethylacrylate were synthesized using acid chlorides (traditional solution reactions), sodium salts of acids (with phase transfer catalysis), and trifluoroacetic anhydride (trifluoroacetate). The interfacial process gave high yields of clean products under very mild conditions. Derivatives obtained include the formate, acetate, hexanoate, stearate, benzoate, trifluoroacetate, and adamantanoate. Bulk polymerizations with 2,2′-azobis (isobutyronitrile) gave high molecular weight polymers with intrinsic viscosities of over 2 dL/g and molecular weights of several million [based on size-exclusion chromatography (SEC) comparison to polystyrene standards]. These high molecular weights were the result of autoacceleration in the bulk as shown by monitoring molecular weight with respect to conversion. Solution polymerization in benzene gave more typical polymer, e.g., the acetate derivative showed an SEC molecular weight of 52,000. Glass transition temperatures for the n-alkyl esters decreased from the formate (77°C) to the hexanoate (15°C); the stearate showed a side-chain melting point of 40°C but no T_g. Glass transitions were observed for the trifluoroacetate, benzoate, and adamantanoate polymers at 69, 130, and 214°C, respectively. Solution ¹³C-NMR showed evidence of tacticity information for the formate and acetate derivatives with appaent preference for syndiotactic polymer formation similar to that of methyl methacrylate. FTIR and solid-state ¹³C-NMR analysis gave spectra with functional group peaks and chemical shift values expected based on composition. The stearate monomer and polymer gave solid-state ¹³C chemical shifts of 34 and 33 ppm, respectively, for the central CH₂ units consistent with monoclinic and orthorhombic crystal packing. © 1994 John Wiley & Sons, Inc.     

In Situ Electrical Network Activation and Deactivation in Short Carbon Fiber Composites via 3D Printing

Prior studies on carbon-filler based, conductive polymer composites have mainly investigated how conductive filler morphology and concentration can tailor a material's electrical conductivity and overlooks the effects of filler alignment due to the difficulty to control and quickly quantify the filler alignment. Here, direct ink write 3D printing's unique ability is utilized to control carbon fiber alignment with a single process parameter, velocity ratio, to instantaneously activate or deactivate the electrical network in composites. Maximum electrical conductivity is achieved by randomly aligning carbon fibers that enhances the chance of direct fiber-to-fiber contact and, thus, activating the electrical network. However, aligning the fibers by increasing the velocity ratio disrupts the electrical network by minimizing fiber-to-fiber contact that resulted in a drastic decrease in electrical conductivity by as much as five orders of magnitude in both short and long carbon fiber composites. With this study, this study demonstrates that electrically conductive or insulative composites can be fabricated sequentially with a single ink. This novel ability to instantaneously control the electrical conductivity of carbon fiber reinforced composites allow to directly embed conductive pathways into designs to 3D print multifunctional composites that are capable of localized heating and self-sensing.     

On the Hydrolytic Stability of Organic Ligands in Al-, Ti- and Zr-Alkoxide Complexes

The complexation degrees of Al-, Ti- and Zr-butoxide (M) with unsaturated and saturated -diketones (3-allylpentane-2.4-dione-APD, acetylacetone-ACAC) and -ketoesters (methacryloxyethyl-acetoacetate-MEAA, allylacetoacetate-AAA, ethylacetoacetate-EAA) as organic ligands (L) were examined by IR and ¹³ C NMR spectroscopy and were found to be L:M 1.5. The hydrolytic stability of the ligands of the metal alkoxide complexes (L:M = 1) during hydrolysis/condensation reactions at the molar ratio h (H₂O : OR) = 0.5–2.0 decreases with increasing H$$₂O:complex ratio. Furthermore, the ligand stability depends on the type of metal in the complexes and decreases in the order Al- > Zr- > Ti-butoxide complexes at h=1. The ACAC ligand likewise shows in the Al-, Ti- and Zr-butoxide complexes a high hydrolytic stability (95–100%) at h=1 within 7 days. The Ti- and Zr-butoxide complexes with -ketoesters as ligand show at h=1> a release to a different extent e.g., up to 60% in the case of the MEAA-ligand in the Ti-butoxide complex after 2 days. In general, the hydrolytic stability of the ligands in the Ti-butoxide complexes (L:M = 1, h=1) decreases in the order ACAC > APD > AAA > EAA MEAA. The hydrolysis/condensation reaction of complexes having a weak ligand stability leads to larger particle sizes in the sols than those with stable ACAC ligands. The results contribute to a more controlled synthesis of sols and of new inorganic-organic hybrid polymers via the sol-gel process.     

Characterization of modified low density lipoprotein subfractions by capillary isotachophoresis

Oxidative modification of low density lipoproteins (LDLs) is an important pathogenetic factor in atherosclerosis. The various steps in oxidative modifications of LDL can be monitored using different methodologies with varying degrees of complexity. In this study, we propose capillary isotachophoresis (CITP) as a suitable tool to detect and measure the degree of oxidation of LDL. LDL was isolated from pooled plasma of healthy volunteers by sequential ultracentrifugation, and oxidation was performed in vitro as well as in cell culture experiments. Native LDL and oxidatively modified LDL were characterized by apo B-100 fluorescence and conjugated diene formation. Samples were separated by CITP combined with sudan black B staining. To underline the inherent advantages of this approach, CITP was compared with classical lipoprotein electrophoresis using agarose gel. We demonstrate the CITP method to be highly sensitive, as changes in peak area of the separated LDL subfractions were detected after only 2 h of oxidation. The leading LDL peaks increased, while the terminating LDL peaks decreased in parallel throughout the duration of oxidation. The LDL samples, oxidized for 4-24 h, also exhibited an increased migration velocity of the fractions. In summary, we present the first study investigating LDL-subfractions separated by CITP and the alterations of these LDL-subfractions after gradual in vitro oxidation and after oxidative modification by monocyte-derived macrophages and vascular smooth muscle cells.