Synthesis of α,β- and β-Unsaturated Acids and Hydroxy Acids by Tandem Oxidation,Epoxidation, and Hydrolysis/Hydrogenation of Bioethanol Derivatives

We report a reaction platform for the synthesis of three different high-value specialty chemical building blocks starting from bio-ethanol, which might have an important impact in the implementation of biorefineries. First, oxidative dehydrogenation of ethanol to acetaldehyde generates an aldehyde-containing stream active for the production of C₄ aldehydes via base-catalyzed aldol-condensation. Then, the resulting C₄ adduct is selectively converted into crotonic acid via catalytic aerobic oxidation (62 % yield). Using a sequential epoxidation and hydrogenation of crotonic acid leads to 29 % yield of β-hydroxy acid (3-hydroxybutanoic acid). By controlling the pH of the reaction media, it is possible to hydrolyze the oxirane moiety leading to 21 % yield of α,β-dihydroxy acid (2,3-dihydroxybutanoic acid). Crotonic acid, 3-hydroxybutanoic acid, and 2,3-dihydroxybutanoic acid are archetypal specialty chemicals used in the synthesis of polyvinyl-co-unsaturated acids resins, pharmaceutics, and bio-degradable/ -compatible polymers, respectively.     

Heat capacity of poly(butylene terephthalate)

The low‐temperature heat capacity of poly(butylene terephthalate) (PBT) was measured from 5 to 330 K. The experimental heat capacity of solid PBT, below the glass transition, was linked to its approximate group and skeletal vibrational spectrum. The 21 skeletal vibrations were estimated with a general Tarasov equation with the parameters Θ₁ = 530 K and Θ₂ = Θ₃ = 55 K. The calculated and experimental heat capacities of solid PBT agreed within better than ±3% between 5 and 200 K. The newly calculated vibrational heat capacity of the solid from this study and the liquid heat capacity from the ATHAS Data Bank were applied as reference values for a quantitative thermal analysis of the apparent heat capacity of semicrystalline PBT between the glass and melting transitions as obtained by differential scanning calorimetry. From these results, the integral thermodynamic functions (enthalpy, entropy, and Gibbs function) of crystalline and amorphous PBT were calculated. Finally, the changes in the crystallinity with the temperature were analyzed. With the crystallinity, a baseline was constructed that separated the thermodynamic heat capacity from cold crystallization, reorganization, annealing, and melting effects contained in the apparent heat capacity. For semicrystalline PBT samples, the mobile‐amorphous and rigid‐amorphous fractions were estimated to complete the thermal analysis. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4401–4411, 2004     

Chain Dominated Orders

We study finite partial orders which have a chain such that every element of the order either belongs to this chain or has all its covers in this chain. We show that such orders are exactly the orders being both interval orders and truncated lattices. We prove that their jump number is polynomially tractable and that their dimension is unbounded. We also show that every order admits a visibility model having such an order as host.     

Synthesis and characterization of poly(vinylcyclohexane) derivatives

Six nearly monodisperse substituted poly(styrene) homopolymers, poly(styrene) (PS), poly(2-methylstyrene) (P2MS), poly(3-methylstyrene) (P3MS), poly(4-methylstyrene) (P4MS), poly(tertiary-butylstyrene) (PtBS), and poly(α-methylstyrene) (FαMS) were anionically polymerized and subsequently saturated using heterogeneous hydrogenation techniques to poly(vinylcyclohexane) (PVCH), poly(2-methylvinylcyclohexane) (P2MVCH), poly(3-methylvinylcyclohexane) (P3MVCH), poly(4-methylvinylcyclohexane) (P4MVCH), and poly(tertiary-butylvinylcyclohexane) (PtBVCH), respectively. In each case, except PαMS, the materials were saturated to > 99% conversion with no chain degradation. PS hydrogenations required the addition of small amounts of tetrahydrofuran to the reaction solvent cyclohexane to enhance miscibility and eliminate large-scale chain degradation. Density gradient and differential scanning calorimetry (DSC) measurements were used to characterize the density and glass transition temperature, T_g, of the unsaturated and saturated polymers. Saturation reduces the density by 3% to 11% and changes T_g substantially. The greatest variation in T_g is obtained with the 3-methyl substituted species where a 63°C increase is observed, while the highest measured T_g is 186°C for P2MVCH. Small-angle neutron scattering (SANS) experiments on binary mixtures of hydrogenous and deuterium labeled PVCH derivatives provided a determination of bulk chain statistics. The statistical segment length is relatively insensitive to vinylcyclohexane ring substitution, except with P3MVCH where a 20% greater value is obtained. ©1995 John Wiley & Sons, Inc.     

An Electrochemiluminescence Assay Based on the Interactionof Diaminotoluene Isomers with Gold(I) and Copper(II) Ions

A novel assay for the determination of 2,4- and 3,4-diaminotoluene (DAT) isomers based on the low-level electrochemiluminescence (ECL) reaction of these molecules with the group IB transition metal ions Au⁺and Cu⁺², respectively, in aqueous solution is described. DAT isomers were screened for ECL against a repertoire of 32 metals, including metal ions such as Cu⁺², Eu⁺³, Mg⁺², Ru⁺³, and Tb⁺³associated with other known ECL complexes, at 1:3 added metal ion:ligand molar ratios. The 1:3 molar ratio presumed tris-bidentate octahedral metal coordination complex formation, which generally yielded optimal ECL intensity. The apparent specificity of Au⁺for 2,4-DAT and Cu⁺²for 3,4-DAT, as indicated by ECL measurements, may be partly based on ionic size as Au⁺has nearly twice the ionic diameter of Cu⁺²and thus may form a coordination complex with themeta,but not theorthoDAT. Other DAT isomers were screened and exhibited mildly enhanced ECL with various metal ions, including group IB transition metal ions, but these ECL enhancements were not statistically significant. In some cases, titration of DAT ligands with Cu⁺²and Au⁺over broad concentration ranges produced nonlinear ECL response curves. Despite low-level ECL, sensitivities in the ppm range for Au⁺, Cu⁺², and their respective DAT isomers were achieved. Time dependence was observed for some of the ECL reactions, including the Ru(III)–bipyridine model system, in which the ECL intensity grew markedly over several hours. No ECL enhancements over background were observed with two dinitrotoluene isomers or an aminonitrotoluene screened against the same set of 32 metals. This novel ECL approach may have applications in the determination of some aminoaromatics from degradation of explosives (e.g., TNT) as well as detection and quantitation of various transition metals in industrial wastewater streams and groundwater supplies. In terms of fundamental science, the present data are probably of interest as an example of size-dependent molecular recognition of metal ions which can be detected by ECL.     

Identification of 2D-gel proteins: a comparison of MALDI/TOF peptide mass mapping to mu LC-ESI tandem mass spectrometry

A comparative analysis of protein identification for a total of 162 protein spots separated by two-dimensional gel electrophoresis from two fully sequenced archaea, Methanococcus jannaschii and Pyrococcus furiosus, using MALDI-TOF peptide mass mapping (PMM) and mu LC-MS/MS is presented. 100% of the gel spots analyzed were successfully matched to the predicted proteins in the two corresponding open reading frame databases by mu LC-MS/MS while 97% of them were identified by MALDI-TOF PMM. The high success rate from the PMM resulted from sample desalting/concentrating with ZipTip(C18) and optimization of several PMM search parameters including a 25 ppm average mass tolerance and the application of two different protein molecular weight search windows. By using this strategy, low-molecular weight (<23 kDa) proteins could be identified unambiguously with less than 5 peptide matches. Nine percent of spots were identified as containing multiple proteins. By using mu LC-MS/MS, 50% of the spots analyzed were identified as containing multiple proteins. mu LC-MS/MS demonstrated better protein sequence coverage than MALDI-TOF PMM over the entire mass range of proteins identified. MALDI-TOF and PMM produced unique peptide molecular weight matches that were not identified by mu LC-MS/MS. By incorporating amino acid sequence modifications into database searches, combined sequence coverage obtained from these two complimentary ionization methods exceeded 50% for approximately 70% of the 162 spots analyzed. This improved sequence coverage in combination with enzymatic digestions of different specificity is proposed as a method for analysis of post-translational modification from 2D-gel separated proteins.     

Synthesis and characterization of core-shell selenium/carbon colloids and hollow carbon capsules

A novel Se/C nanocomposite with core-shell structures has been prepared through a facile one-pot microwave-induced hydrothermal process. The new material consists of a trigonal-Se (t-Se) core and an amorphous-C (a-C) shell. The Se/C composite can be converted to hollow carbon capsules by thermal treatment. These products were characterized by transmission electron microscopy (TEM), powder X-ray diffraction (XRD), scanning electron microscopy (SEM), selected area electron diffraction (SAED), energy-dispersive X-ray (EDX) spectroscopy, and X-ray photoelectron spectroscopy (XPS).     

Selective O‐allylation of bisphenol A: toward a chloride‐free route for epoxy resins

The O‐allylation of bisphenol A (BPA) has been performed with the most selective catalysts for O‐allylation of phenols reported previously. Both the cyclopentadienyl–ruthenium catalysts and the palladium–diphosphine catalysts are capable of selectively performing single and double O‐allylation of BPA. An intriguing solvent effect is observed; the choice of the solvent is of key importance for both conversion and selectivity. The use of an excess of diallyl ether as allylating agent results in relatively high yields of the bisallyl ether of bisphenol A, while maintaining the high selectivity for O‐allylation. Copyright © 2010 John Wiley & Sons, Ltd.